Polycationic viscoelastic compositions

ABSTRACT

Viscoelastic compositions are disclosed herein containing an effective amount of one or more random or structurally defined polycationic quaternary ammonium compounds for controlling the viscoelasticity of the composition. In at least one aspect, the present technology provides polycationic quaternary ammonium compounds comprising bis-quaternary compounds. In another aspect, the present technology provides viscoelastic compositions that comprise polycationic quaternary ammonium compounds comprising bis-quaternary compounds. Preferred viscoelastic compositions of the present technology maintain viscoelasticity at a temperature greater than about 80° C., preferably greater than about 100° C. or about 110° C. when the amount of the one or polycationic quaternary compounds is less than about 10% by weight based on the total weight of the composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of a PCT Application No.PCT/US06/43384, filed on Nov. 7, 2006, which claims the benefit of U.S.Provisional Application Ser. No. 60/734,465, filed on Nov. 7, 2005. Thecontents of the above-identified applications are hereby incorporated byreference to provide continuity of disclosure.

FIELD OF THE INVENTION

The presently described technology generally relates to polycationicquaternary ammonium compounds and polycationic viscoelastic compositionsmade therewith. Polycationic viscoelastic compositions of the presenttechnology are suitable for use in a variety of applications whereviscoelasticity is a desirable characteristic. Examples of suchapplications include, for example, hydraulic fluids, demulsifiers,foamers, organoclays, thickeners, biocides, and oil field fluids.

One or more preferred polycationic viscoelastic compositions of thepresent technology impart useful theological properties to aqueoussolutions at relatively low concentrations of active ingredients (e.g.,gemini quaternary compounds). Useful theological properties provided byone or more preferred compositions of the present technology include,for example, viscoelasticity, increased viscosity, shear-thinning, anddrag reduction in moving fluids.

BACKGROUND OF THE INVENTION

Some examples of bis-quaternary or polycationic quaternary ammoniumcompounds have been studied and reported. For example, U.S. Pat. No.4,734,277, to Login, issued on Mar. 29, 1988, describes the preparationof certain bis-quaternary compounds by reacting tertiary amines with asuitable epoxide, such as epichlorohydrin, and further discloses thatthe resulting bis-quaternary ammonium compounds have utility as anadditive in cosmetics applications, such as hair conditioners, skinlotions, etc.

For another example, U.S. Pub. Pat. Appl. 2004/0067855, to Hughes, etal., published on Apr. 8, 2004, discloses certain bis-quaternary oroligomeric cationic quaternary ammonium compounds useful in aviscoelastic well bore treatment fluid for controlling theviscoelasticity of that fluid.

Hydrocarbons such as oil, natural gas, etc., are obtained from asubterranean geologic formation by drilling a well that penetrates thehydrocarbon-bearing formation. This drilling outcome provides a partialflow path for the hydrocarbon, typically oil, to reach the surface. Inorder for oil to travel from the formation to the well bore (andultimately to the surface), there must be a sufficiently unimpeded flowpath through the rock formation (e.g., sandstone, carbonates), whichgenerally occurs when rock pores of sufficient size and number arepresent.

A common impediment to oil production is “damage” to the formation,which plugs the rock pores and impedes the flow of oil. Moreover,depletion of zones nearest to the well bore causes a gradual decline inproduction. Generally, techniques used to increase the permeability ofthe formation and to provide extended conduits to the well bore arereferred to as “stimulation.” Aqueous gels are often used in differentwell stimulation processes.

For example, in a fracturing process, which is one kind of wellstimulation technique, cracks or fissures (fractures) are created insubterranean formations. Gels are used in fracturing processes as themedium which transfers energy from outside the subterranean formation tothe specific locations inside the subterranean formation in order tocreate the desired fractures. The energy to create the fractures istransferred primarily as pressure against the formation, by pumping thefracturing fluid into the well bore where it is directed to desiredportions of the subterranean formation. The gels are relativelyincompressible fluids, and pressure is exerted against the subterraneanformation until the force is sufficient to fracture the formation. Oncethe fracture is created, the high viscosity of the gel is important asit flows into the newly formed cracks and fissures. As the fracturingfluid flows into the fracture, it carries proppant (e.g., smallparticles of sand, ceramics, or other hard material) into the fracture.Once the force from pumping the fracturing fluid is removed, theproppant remains in the fractures, which prevents the fractures fromclosing. The fracturing fluid is then removed from the well bore, andthe well bore is prepared for recovering further amounts ofhydrocarbon(s).

Older technology utilizes polysaccharide polymers to form the aqueousgels utilized as fracturing fluids. Often, the polysaccharide gels arecross-linked using additives such as titanates, zirconates or borates.Once the fracturing process is complete, these gels normally require aseparate process to remove them from the well bore, which typicallyrequires a significant amount of time and additional well treatmentchemicals. Furthermore, complete removal of the polymer gel is seldomattainable, and the polymer that remains in the well bore can clog thepores of the rock formation, thus preventing hydrocarbon from flowingthrough and from the pores.

Non-polymeric gellants (NPGs) are more recent technological developmentsthat provide alternatives to polysaccharide gels. NPGs are surfactants,and usually are quaternary ammonium compounds (cationic) or amphotericcompounds. Particularly desired NPGs form viscoelastic solutions (VESs)because certain properties of VESs prove useful for well stimulationprocesses. One such property is the ability of a VES to support proppantat lower viscosities than a polymer solution. Another useful property isthe reduction of friction between the moving fluid and the surfacescontacted therewith. An especially useful feature of VES gels is that,on contact with hydrocarbons, the gels break with a resultant sharp dropin viscosity. At the lower viscosity, removal of the fracturing fluidfrom the well bore requires no additional well treatment chemicals, andrequires less time and equipment than do polymeric gellants. NPGsurfactant gels may also be broken by other means. Furthermore, unlikepolysaccharide gellants, NPGs have substantially less tendency to clogthe hydrocarbon-producing pores in the subterranean formation.

NPGs are also useful in other well treatment applications. For example,they can reduce the loss of fracturing fluid into subterraneanformations; reduce the production of water from wells; form gels forwell bore cleaning; and reduce friction between flowing solutions andsolid objects.

The application of viscoelastic surfactants in both non-foamed andfoamed fluids used for fracturing subterranean formations has beendescribed in several patents, e.g., EP 0835983 B1, to Brown et al.,issued Dec. 17, 2003; U.S. Pat. No. 5,258,137, to Bonekamp et al.,issued on Nov. 2, 1993; U.S. Pat. No. 5,551,516, to Norman et al.,issued on Sep. 3, 1996; U.S. Pat. No. 5,964,295, to Brown et al., issuedon Oct. 12, 1999; and U.S. Pat. No. 5,979,557 to Card et al., issued onJun. 16, 1999.

The use of viscoelastic surfactants for water shut off treatments andfor selective acidizing is discussed in British Patent Application No.GB 2332224 A, to Jones et al., published on Jun. 16, 1999; and Chang F.F., Love T., Affeld C. J., Blevins J. B., Thomas R. L. and Fu D. K.,“Case study of a novel acid diversion technique in carbonatereservoirs”, Society of Petroleum Engineers, 56529, (1999).

More recent developments in this field can be found in U.S. Pub. Pat.App. No. 2004/0102330 A1, to Zhou, et al., published on May 27, 2004,which describes cleavable monomeric VES surfactants; and U.S. Pub. Pat.App. No. 2004/0067855 A1, to Hughes, et al., published on Apr. 8, 2004,which describes oligomeric anionic or cationic VES surfactants(including dimeric and trimeric forms).

Conventional cationic NPGs used in the hydrocarbon recovery fieldutilize alkyl amines with a single hydrophobic carbon chain. To beuseful in fracturing applications, the hydrophobe chains of conventionalcationic NPGs are preferably and predominantly 18 carbon atoms inlength, and more preferably greater than 18. An example of one suchcommercially available material is ClearFRAC™, commercially availablefrom Schlumberger-Doll Research (“Schlumberger,” Ridgefield, Conn.),i.e., erucyl-N,N-di-(2-hydroxyethyl)-N-methylammonium chloride (EHMAC),which is asserted to provide performance at the highest applicationtemperatures (up to about 250° F. (about 121° C.)) of any currentlycommercially available viscoelastic fracturing fluid. This productreportedly contains less than 3% hydrophobe carbon chains of 18 carbonsor less. Because the intermediate used to make EHMAC must be purified toremove the components with alkyl chains of 18 carbons or less, EHMACcosts substantially more to produce than other alkyl amine cationicmaterials. The high cost of EHMAC limits the number of stimulationprocesses for which it is used on a repeated basis.

A commercially available alternative to ClearFRAC™ is AquaClear™surfactant fracturing fluid, commercially available from BJ ServicesCompany (“BJ Services”, Huston, Tex.). It also uses a quaternaryalkylamine, but is less costly because an extensively purifiedintermediate is not required. However, the maximum applicationtemperature for AquaClear™ is about 170° F. (about 76.7° C.), which issubstantially lower than ClearFRAC™'s 250° F. (about 121° C.).

While having some obvious advantages over polysaccharide gels,conventional NPG gels also have some disadvantages. One is thetemperature limitation of conventional NPG surfactant gels. As welldepth increases, well bore hole temperature usually also increases, andmay frequently exceed 250° F. (about 121° C.). Currently, conventionalNPG surfactant technology fails under these conditions, whilepolysaccharide gels continue to perform. Another disadvantage is cost,in that the material cost for polysaccharide gels is substantially lowerthan that for NPG surfactant gels.

Yet another disadvantage of conventional NPG surfactants is theirtoxicity to the environment and their poor biodegradability. Becausecationic alkylamines do not breakdown readily in the environment, theytend to accumulate. Alkylamine quaternary compounds are also toxic tomany life forms, so they can have a destructive impact, particularly onenvironments in which they accumulate. Some areas of the world haveimposed regulatory restrictions on chemicals based on their beinghazardous to the environment. For example, in the North Sea, chemicalssuch as cationic alkylamine are either restricted or banned entirely.

Thus, there is a need for gellants, in particular, viscoelasticgellants, that can provide all or most of the advantages of theconventional NPG technology, and that (1) can provide viscoelasticproperties at higher temperatures (greater than 80° C. or 176° F., andpreferably greater than 110° C. or 230° F.); (2) are more eco-friendly;and/or (3) are more cost effective. The presently described technologyaddresses these needs.

BRIEF SUMMARY OF THE INVENTION

It has been surprisingly found that polycationic quaternary ammoniumcompounds of the presently described technology that have at least twocationic sites connected through a linker can be used as activeingredients to form viscoelastic compositions with distinctive anduseful properties.

In one aspect, the presently described technology provides viscoelasticcomposition comprising water and at least one polycationic quaternaryammonium compound to control the viscoelasticity of the composition,wherein the at least one polycationic quaternary ammonium compoundcomprises a bis-quaternary compound of the following general formula:

In the formula above, R₂, R₃, R₄, and R₅ can be members independentlyselected from: (a) hydrocarbyl groups having from about 1 to about 4carbon atoms; or (b) substituted hydrocarbyl groups having from about 1to about 4 carbon atoms. Alternatively, R₂ and R₃ can be members of aheterocyclic ring, and R₄ and R₅ can be members of a differentheterocyclic ring or are independently selected from group (a) asdefined above or group (b) as defined above. Also, in the formula above,R₇ can be a member selected from hydrocarbyl groups having from about 2to about 30 carbon atoms, or substituted hydrocarbyl groups having fromabout 2 to about 30 carbon atoms. Further, R₁ and R₆ can be membersindependently selected from: group (a) as defined above; group (b) asdefined above, or (c) hydrocarbyl groups having from about 13 to about40 carbon atoms or substituted hydrocarbyl groups having from about 13to about 40 carbon atoms. At least one of R₁ or R₆ is a member of group(c) as defined above. A₁ ⁻ and A₂ ⁻ are independently selected from: (i)negatively charged inorganic ions; (ii) organic molecules with one ormore negatively charged functional groups; or (iii) negatively chargedfunctional groups which are part of R₁, R₂, R₃, R₄, R₅, R₆, or R₇.

It should be appreciated that bis-quaternary compounds of the presenttechnology can be symmetric or dissymmetric.

Further, the components of bis-quaternary compounds of the presenttechnology can be derived from any suitable fatty acid source, such asanimal, vegetable or hydrocarbon sources. As described herein, preferredembodiments of various components are derived from animal or vegetablefatty acid sources.

Moreover, hydrocarbyl or substituted hydrocarbyl groups for thepresently described technology can be aliphatic, aromatic, acyclic orcyclic.

Certain viscoelastic compositions of the present technology can be usedin, for example, well bore treatment fluids, drilling fluids,thickeners, completion fluids, diversion fluids, and many otherapplications where thickened or gelled aqueous compositions are desired.For example, some embodiments of the viscoelastic compositions of thepresent technology can be used in personal care compositions. In atleast one embodiment, the present technology provides a clearviscoelastic composition comprising water and least one polycationicquaternary ammonium compound comprising a bis-quaternary compound of thepresent technology.

Compared with conventional viscoelastic surfactants, one advantage of atleast some embodiments of polycationic quaternary ammonium compounds(polycationic “quats”) of the presently described technology is thatthey utilize substantially lower cost, commodity or readily availableraw materials. For example, in at least some embodiments, at least oneof R₁ or R₆ is derived from a carboxylic acid derived from an animal orvegetable oil.

The amount of polycationic quaternary ammonium compounds of the presenttechnology in a viscoelastic composition should be sufficient to providethe viscoelasticity needed for the composition and application desired.For example, in some embodiments, the amount of polycationic quaternaryammonium compound is less than about 10% by weight based on the totalweight of the viscoelastic composition. Current commercial systems tendto use polycationic quats in amounts of 3% to 4% by weight, and certainpreferred embodiments of the present technology thus offer the advantageof requiring lower quantities of polycationic quats to achievecomparable or noticeably higher composition viscosities.

Compared with conventional VES surfactants, preferred polycationic quatsof the present technology also tend to have higher viscosities at highertemperatures. Preferably the viscoelasticity of such compositions can bemaintained at a temperature of at least about 80° C. alternatively atgreater than about 80° C., such as at temperatures of about 85° C.,about 90° C., about 95° C., or higher. More preferably, theviscoelasticity of such compositions can be maintained at a temperatureof at least about 100° C., alternatively at greater than about 100° C.Most preferably the viscoelasticity of such compositions can bemaintained at a temperature of at least about 110° C., alternatively atgreater than about 110° C. Therefore, the useful working temperatures ofwell bore treatment fluids based on the present technology, for example,can be increased as compared to the useful working temperatures of wellbore treatment fluids based upon conventional technology.

At least some embodiments of viscoelastic gels of the present technologycan be prepared by using methods in current commercial practice (e.g.,combining polycationic compounds of the present technology withpotassium chloride (KCl) or sodium xylene sulfonate (SXS)), or by usingthe active ingredient in water without additives in some cases.

Further, one or more preferred embodiments of the polycationic quats ofthe present technology are more susceptible than conventional alkylaminecationic compounds to natural chemical degradation processes such ashydrolysis, so they degrade in the environment faster than do alkylaminecationic compounds. Therefore, some embodiments of preferred chemicalcompounds of the present technology are expected to be lessenvironmentally harmful and accumulate less in the environment than doalkylamine cationics, for example.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is a schematic representation of at least one bis-quaternaryammonium compound of the present technology consisting of one linkerfragment and two cationic fragments, wherein the two cationic fragmentsare either the same or different and randomly joined.

FIG. 2 is a schematic representation of a method of making a randomgemini quat from two tertiary amines and a substrate to provide thelinker. FIG. 2 also shows that the linker in the gemini quat can besubsequently modified to produce a modified gemini quat.

FIG. 3 is a schematic representation of at least one structurallydefined bis-quaternary ammonium compound of the present technology,wherein the two cationic fragments are different.

FIG. 4 is a schematic representation of at least one step-wise method ofmaking a structurally defined bis-quaternary ammonium compound of thepresent technology, wherein the substrate to provide the linker is anepihalohydrin.

FIG. 5 a shows flow curves of a VES containing 3% EHMAC in 4% KCl (wt/wt%).

FIG. 5 b shows a molecular structure of EHMAC.

FIG. 6 a shows flow curves of a VES containing 3% geministearamidopropyldimethyl-ammonium di-chloride (18APDMA-3(OH)-18-APDMA orSAPDMA GQ) in 1.5% KCl (wt/wt %).

FIG. 6 b shows a molecule structure of SAPDMA GQ.

FIG. 7 a shows flow curves of a VES containing 3% gemini(cetyl/oleyl)amidopropyl-dimethylammonium di-chloride ((16APDMA/18:1APDMA)-3-(OH)-(16APDMA/18:1 APDMA)) in 1.5% KCl (wt/wt %).

FIG. 7 b shows a molecule structure of (16APDMA/18:1APDMA)-3-(OH)-(16APDMA/18:1 APDMA).

FIG. 8 a shows flow curves of a VES containing 3% dissymmetric geminioleamidopropyldimethylammonium-stearamidopropyl-dimethylammoniumdi-chloride ((18:1 APDMA)-3-(OH)-18-APDMA) in 1.5% KCl (wt/wt %)

FIG. 8 b shows a molecule structure of (18:1 APDMA)-3-(OH)-18-APDMA.

FIG. 9 a shows flow curves of a VES containing 3% dissymmetric geminisoyamidopropyldimethylammonium-stearamidopropyl-dimethylammoniumchloride toluene sulfonate (SoyAPDMA-3-(OH)-18APDMA) in 0.75% KCl (wt/wt%).

FIG. 9 b shows a molecule structure of SoyAPDMA-3-(OH)-18APDMA.

FIG. 9 c shows flow curves of a VES containing 1.25%SoyAPDMA-3-(OH)-18APDMA in 1.5% KCl (wt/wt %).

FIG. 10 a shows flow curves of a VES containing 3% gemini high erucicrapeseed amidopropyldimethylammonium di-chloride(HERAPDMA-3-(OH)—HERAPDMA or HERAPDMA GQ) in 0.5% SXS (wt/wt %).

FIG. 10 b shows a molecule structure of HERAPDMA GQ.

FIG. 10 c shows flow curves of a VES containing 2% HERAPDMA GQ in 1.5%KCl (wt/wt %).

FIG. 11 a shows flow curves of a VES containing 3% dissymmetric geminibehenamidopropyldimethylammonium-high erucic rapeseedamidopropyldimethyl-ammonium di-chloride (22APDMA-3-(OH)—HERAPDMA).

FIG. 11 b shows a molecule structure of 22APDMA-3-(OH)—HERAPDMA.

FIG. 12 a shows flow curves of a VES containing 4% of the dissymmetricBQ shown in FIG. 12 b in 25% CaCl₂ (wt/wt %).

FIG. 12 b shows a molecule structure of dissymmetric bis-quaternary (BQ)high erucic rapeseed amidopropyl-dimethylammonium-triethylammoniumdi-chloride.

FIG. 12 c shows flow curves of a VES containing 2.5% of the dissymmetricBQ shown in FIG. 12 b in 25% CaBr₂ (wt/wt %).

FIG. 12 d shows flow curves of a VES containing 2.75% of thedissymmetric BQ shown in FIG. 12 b in 6% CaBr₂ (wt/wt %).

FIG. 13 a shows flow curves of a VES containing 3% of the PCC shown inFIG. 13 b in deionized water (wt %).

FIG. 13 b shows a molecule structure of poly-cationic carboxylate (PCC)bis-high erucic rapeseed amidopropyldimethylammonium di-chloridephthalate half-ester, triethylammonium salt.

FIG. 14 shows vesicles of relatively uniform size distribution formed byhydration of a film of C65-GQ using 0.1 wt % CaCl₂. The magnification is200×.

FIG. 15 shows vesicles being generated from a dried film of C65-GQ byhydration with 0.1% sodium xylene sulfonate.

DETAILED DESCRIPTION OF THE INVENTION Definitions and Conventions

As used herein, the term “acyclic” pertains to aliphatic compoundsand/or groups which are linear or branched, but not cyclic (also knownas “open-chain” groups).

As used herein, the term “alicyclic” pertains to compounds and/or groupswhich have one ring, or two or more rings (e.g., spiro, fused, bridged),wherein said ring(s) are not aromatic.

As used herein, the term “aromatic” pertains to unsaturated compoundswith at least one closed ring of at least 5 atoms, with all of the ringatoms being co-planar or almost co-planar and covalently linked, andwith all of the ring atoms being part of a mesomeric system. As usedherein, when the “aromatic” substituent is monocyclic, it preferablycontains 5 or 6 ring atoms, and when the “aromatic” substituent ispolycyclic, it preferably contains 9 or 10 ring atoms contained in fusedrings.

As used herein, the terms “carbo,” “carbyl,” “hydrocarbon” and“hydrocarbyl”, pertain to compounds and/or groups which have only carbonand hydrogen atoms.

As used herein, the term “cyclic” pertains to compounds and/or groupswhich have one ring, or two or more rings (e.g., spiro, fused, bridged).Compounds with one ring may be referred to as “monocyclic” or“mononuclear” whereas compounds with two or more rings may be referredto as “polycyclic” or “polynuclear.”

As used herein, the term “heterocyclic” pertains to cyclic compoundsand/or groups which have one heterocyclic ring, or two or moreheterocyclic rings (e.g., spiro, fused, bridged), wherein said ring(s)may be alicyclic or aromatic.

As used herein, the term “heterocyclic ring” pertains to a closed ringof from about 3 to about 10 covalently linked atoms, more preferablyabout 3 to about 8 covalently linked atoms, wherein at least one of thering atoms is a multivalent ring heteroatom, for example, nitrogen,phosphorus, silicon, oxygen, and sulfur, though more commonly nitrogen,oxygen, and sulfur.

As used herein, the term “hydrophobe” refers to hydrophobic segments ofatoms in molecules that include a straight or branched hydrocarbon chainof five or more carbon atoms.

As used herein, the term “polycationic” pertains to molecules that havetwo or more atoms which have a positive electrical charge, preferably atall pHs.

As used herein, the term “ring” pertains to a closed ring of from about3 to about 10 covalently linked atoms, more preferably about 5 to about7 covalently linked atoms.

As used herein, the term “saturated” pertains to compounds and/or groupswhich do not have any carbon-carbon double bonds or carbon-carbon triplebonds.

As used herein, a “substitution reaction” is defined according to theIUPAC Compendium of Chemical Terminology as “a reaction, elementary orstepwise, in which one atom or group in a molecular entity is replacedby another atom or group.”

As used herein, the term “unsaturated” pertains to compounds and/orgroups which have at least one carbon-carbon double bond orcarbon-carbon triple bond.

As used herein, “viscoelastic” composition (e.g., solution, fluid, orgel), means the elastic (or storage) modulus G′ of the composition isequal to or greater than the loss modulus G″ as measured using anoscillatory shear rheometer (such as a Bohlin CVO 50 or TA InstrumentsAR2000) at least one frequency between 0.0001 Hz and 1 Hz and at 20° C.The measurement of these moduli is further described in “An Introductionto Rheology,” by H. A. Barnes, J. F. Hutton, and K. Walters, Elsevier,Amsterdam (1997). The disclosure of such measurements in “AnIntroduction to Rheology” is hereby incorporated by reference.

DESCRIPTION OF THE INVENTION

While the presently described technology is described herein inconnection with one or more preferred embodiments, it should beunderstood that it is not limited to those embodiments. On the contrary,the presently described technology includes all alternatives,modifications, and equivalents to those embodiments as may be includedwithin the spirit and scope of the appended claims.

In a first aspect, the presently described technology relates toviscoelastic compositions of polycationic quats that have at least twocationic sites. The cationic sites of polycationic quats of the presenttechnology are quaternary ammonium chemical functional groups. Themolecules of the polycationic quats can also have other chemicalfunctional groups. Additionally, the molecules of the polycationic quatscan be symmetric or dissymmetric. Each cationic functional group isconnected to another cationic functional group by a “linker,” and anexample of such an arrangement is illustrated by FIG. 1.

In most cases, each linker is derived from a molecule which is capableof undergoing two or more substitution reactions. The linker may be thesubstrate of a molecule in a substitution reaction of the molecule withan amine, though the linker may itself have amine functional groups.

In accordance with at least one embodiment of the present technology, inthe substitution reaction, a nitrogen atom of an amine becomes bonded toa carbon atom of the linker precursor molecule. In this substitutionreaction, the amine nitrogen that forms a bond with the substrate carbonatom may be referred to as the “nucleophile,” while the atom or groupthat becomes detached from an atom of the substrate is called the“leaving group.” However, it is not necessary for the leaving group tobecome detached from the substrate completely. It is only needed tobecome detached from the carbon atom which becomes attached to the aminenitrogen for a sufficient number of molecules.

A person of ordinary skill in the art will understand that an aminenitrogen may be capable of undergoing more than one such substitutionreaction. In general, the number of times an amine nitrogen can undergoa substitution reaction is equal to the number of hydrogen atoms bondedto the nitrogen of the free amine plus one. For purposes of discussionin this disclosure, the number of times an amine nitrogen mayparticipate in a substitution reaction is referred to as its theoreticalfunctionality (“F”) (which is different from chemical functionalgroups). Amines that can themselves become linkers have theoreticalfunctionality of about 2 or more. With mixtures of amines with differenttheoretical functionality, an expression of “average functionality” isuseful. Average functionality is simply the equivalents of a reactivegroup divided by the moles of reactive molecules:Average Functionality=(total equivalents of theoreticalfunctionalities)/(total moles).

Thus, an equal molar mixture of dimethylamine, with a functionality of2, and trimethylamine, with a functionality of 1, has an averagefunctionality of 1.5. These concepts are important for insights intosuch phenomena as chain branching and chain termination in cases wherenon-quaternary amines are linkers, or in higher polycationic quats,where polycationic quats may become multi-chained and highly networked.

When the leaving group is negatively charged, it can be called anucleofuge. A nucleofuge may remain in the viscoelastic composition ofthe present technology as the negative counter ion (anion) to aquaternary ammonium cation. A nucleofuge may also be convertedchemically to another anion, or it may be exchanged with anions from anexternally supplied source. A net electrical charge of zero ismaintained by the presence of counter ions (anions) in a polycationiccomposition. The counter ions to the quaternary ammonium cations of thepresent technology can be one or more negatively charged inorganic atomsor functional groups of atoms, and can be from one or more negativelycharged organic molecules.

A linker in the polycationic quat molecule may be hydrophilic,hydrophobic or essentially neither. The presence of both electricallycharged and/or polar atoms (which are hydrophilic) and hydrophobe(s) inthe linker promotes the surface activity of the molecule. Preferredlinkers are hydrophilic, in that the have atoms capable of forminghydrogen bonds with water or other polar molecules.

Viscoelastic compositions of the present technology, such asviscoelastic solutions (VESs) or gels, can be prepared by combiningpolycationic quats of the present technology with water, and optionallywith additional additives, such as inorganic salts, anionic hydrotropesor surfactants, or other useful organic compounds (such as carboxylic orpolycarboxylic acids). The order of mixing is typically not particularlyimportant to achieving a viscoelastic composition.

Typically, viscoelastic solutions and gels are prepared throughdissolution of gellant compounds in base solutions. Any suitablemechanical means for obtaining a homogeneous solution is acceptable.Base solutions normally provide the bulk of the viscoelastic solutionsor gels, typically up to about 90% or greater by weight. Base solutionscan comprise water. Base solutions can also contain salt(s), and canhave up to about 65 wt % salt. Metal (or ammonium) halide salts are usedmost commonly, but other inorganic mineral acid salts may also be used.Alternatively, the base solution may be a polar organic compounddissolved in water. Non-exhaustive examples of such compounds includesalicylic acid (or salts thereof), phthalic acids (or salts thereof), ororganic sulfonic acids (or salts thereof).

When preparing viscoelastic gels, air bubbles are frequently trapped inthe gels and should be removed before accurate viscosity measurementscan be made. Centrifugation, ultrasonication in warm water baths, andheating in ovens at between about 70° C. and about 80° C. overnight canbe used to induce bubble-free gels.

In at least some aspects, polycationic quats of the present technologycan be provided in the form of a concentrated solution in an organicsolvent (e.g., alcohols, ketones, or glycol ethers) before being mixedwith water to make an aqueous viscoelastic composition for a specificapplication. For example, when used as a gelling agent, the polycationicquats of the present technology can first be dissolved in an alcohol,such as isopropyl alcohol, preferably with some water, to make aconcentrated solution, in which the concentration of the activeingredient can be made as high as possible while maintaining desirablehandling properties, such as fluidity. Suitable concentrations of thepolycationic compound can range from about 20% to about 60%, or higher,by weight. The concentrated polycationic compound solution can then beadded to water, or a water solution of salt, organic acids, etc., withmixing to make a viscoelastic composition (such as a solution or gel)containing an effective amount of the polycationic quats of the presenttechnology suitable for use in one or more oil field applications.

Particularly when used as well bore fluids, viscoelastic compositions ofthe presently described technology are generally thickened aqueouscompositions, and preferably comprise less than about 10 wt % ofpolycationic quats of the present technology. For example, in someembodiments, viscoelastic compositions can comprise from about 5 wt % toabout 8 wt % of polycationic quats of the present technology. Morespecifically, preferred viscoelastic compositions of the presenttechnology can comprise any amount of polycationic quats of the presenttechnology less than about 10 wt %, such as about 8 wt %, about 6 wt %,about 5 wt %, about 4 wt %, about 3 wt %, about 2.5 wt %, about 2 wt %,about 1.5 wt %, or about 1 wt %. In some embodiments, viscoelasticcompositions of the present technology comprise less than about 1 wt %polycationic quats, such as about 0.75% wt %, about 0.5 wt %, about 0.25wt %, or about 0.1 wt %. Some viscoelastic compositions of the presenttechnology comprise from about 0.1 wt % to about 5 wt %, from about 0.25wt % to about 4 wt %, from about 0.25 wt % to about 3 wt %, or fromabout 1.0 wt % to about 2.0 wt % of polycationic quats of the presenttechnology.

Additives, such as inorganic salts (electrolytes), organic acids, saltsof organic acids, poly acids, salts of poly acids, diacids, salts ofdiacids, anionic surfactants, anionic hydrotropes, poly-anionicpolymers, or combinations thereof, can be added to viscoelasticcompositions of the present technology depending on the demands of theparticular application. Some additives can impart higher viscosities toviscoelastic solutions at elevated temperatures, as compared to the samesystems without these additives. However, additives are not required inall applications and compositions of the present technology.

Inorganic salts that can be useful as additives in viscoelasticcompositions include, for example, halide salts (predominantly bromidesand chlorides) of alkali metals (such as sodium, potassium, cesium) oralkaline earth metals (such as calcium and magnesium). Some preferredinorganic salts for use in viscoelastic solutions of the presenttechnology include, but are not limited to, sodium chloride (NaCl),potassium chloride (KCl), ammonium chloride (NH₄Cl), calcium chloride(CaCl₂), sodium bromide (NaBr), calcium bromide (CaBr₂), and zincbromide (ZnBr₂), potassium formate (KHCOO), cesium chloride (CsCl),cesium bromide (CsBr), or combinations thereof.

Examples of other additives can include organic acids (e.g., carboxylicor sulfonic acid), diacids, polyacids, and salts of these acids. Organicmolecules bearing negative charge(s), typically derived from organicacids can be used to provide organic counter ions. For example,ortho-phthalate salts can be prepared by mixing o-phthalic anhydride inwater with bases, such as alkali metal hydroxides (NaOH or KOH) ortertiary amines (e.g. triethylamine). The organic acids, or their salts,may also be present as pendant groups on polymer chains. Such polymersare referred to herein as poly-anionic polymers.

Hydrotropes are also useful in certain circumstances. Examples ofsuitable hydrotropes can include sodium xylene sulfonate (SXS), sodiumcumene sulfonate (SCS), and ammonium xylene sulfonate (AXS). Anionicsurfactants may also provide desirable properties in conjunction withcertain polycationic quats of the present technology used as activeingredients.

In some preferred embodiments of the present technology for use asviscoelastic well bore treatment fluids in oil fields, such fluidscontain viscoelastic compositions as described above, such ascompositions of water and at least one polycationic quaternary ammoniumcompound of the present technology to control the viscoelasticity of thecomposition. In some such embodiments, well bore treatment fluids of thepresent technology further comprise a proppant. Proppants suitable foruse with the present technology can be, but are not limited to, smallparticles of sand, ceramics, or other hard materials.

Polycationic quats of the present technology tend to have higherviscosities at higher temperatures as compared to conventional NPGs. Inone or more preferred embodiments, the polycationic quats of the presenttechnology provide viscoelasticity such that the viscoelasticcompositions of the present technology maintain viscoelasticity at atemperature of at least about 80° C., or greater than about 80° C., suchas at temperatures of about 85° C., 90° C., 95° C., or higher. Morepreferably, the viscoelasticity of viscoelastic solutions of the presenttechnology can be maintained at a temperature of at least about 100° C.,or greater than about 100° C. Most preferably, the viscoelasticity ofviscoelastic solutions of the present technology can be maintained at atemperature of at least about 110° C., or greater than about 110° C.

Random Bis-Quaternary Ammonium Compounds

Bis-quaternary ammonium compound (“bis-quat”) molecules that have twoquaternary ammonium atoms and two or more hydrophobes are commonlycalled “gemini” quaternary compounds, and may be referred to as GQshereafter.

In accordance with some embodiments, the presently described technologyprovides viscoelastic compositions containing at least one GQ resultingfrom random substitution reactions. Such a viscoelastic composition canbe called a “random GQ” composition. In the substitution process, theamine nitrogen atoms are quaternized and become cationic.

The following formula illustrates a general structure of a bis-quatmolecule used in the random bis-quat compositions of this embodiment:

In some embodiments of bis-quat molecules of the present technologyhaving this general structure, R₂, R₃, R₄, and R₅ can be membersindependently selected from (a) hydrocarbyl groups having from about 1to about 4 carbon atoms, or (b) substituted hydrocarbyl groups havingfrom about 1 to about 4 carbon atoms. Alternatively, R₂ and R₃ can bemembers of a heterocyclic ring, preferably a heterocyclic ringcontaining 5 or 6 carbon atoms. In such embodiments, R₄ and R₅ can bemembers of a different heterocyclic ring, or can be independentlyselected from group (a) as defined above or group (b) as defined above.When R₄ and R₅ are members of a different heterocyclic ring, that ringpreferably contains 5 or 6 carbon atoms.

Additionally, in some embodiments of such bis-quat molecules of thepresent technology, R₁ and R₆ can be members independently selected fromgroup (a) as defined above, group (b) as defined above, or (c)hydrocarbyl groups having from about 13 to about 40 carbon atoms orsubstituted hydrocarbyl groups having from about 13 to about 40 carbonatoms. In some such embodiments, the hydrocarbyl groups or substitutedhydrocarbyl groups of group (c) can comprise carboxamides, carboximides,polycarboxamides, polycarboximides, carboxamidines, carboximidines,carboxylic esters, polycarboxylic esters, carboxylic acids,polycarboxylic acids, carboxylates, polycarboxylates, or combinationsthereof.

In some particularly preferred embodiments, at least one of R₁ or R₆ isa member of group (c), and in some such embodiments, can furthercomprise a cyclo hydrocarbyl ring or a heterocyclic ring. In someembodiments, R₁ and R₆ are both chosen from group (c), while in others,only R₁ or R₆ is chosen from group (c). In at least one embodiment, R₁is selected from group (c) and R₆ is selected from group (a) or group(b). In at last one embodiment, each of R₄, R₅, and R₆ is a hydrocarbylgroup having from about 1 to about 4 carbon atoms or a substitutedhydrocarbyl group having from about 1 to about 4 carbon atoms. In somepreferred embodiments, at least one of R₁ or R₆ is derived from acarboxylic acid having from about 13 to about 40 carbon atoms, and morepreferably from about 16 to about 22 carbon atoms. In some particularlypreferred embodiments, the carboxylic acid is derived from an animal orvegetable oil.

When at least one of R₁, R₂, or R₃ and at least one of R₄, R₅ or R₆ arehydrophobes, the bis-quat is a gemini-quat (GQ).

The hydrocarbyl groups of groups (a), (b) and (c) can be arranged in anychemically rational combination, including aliphatic, aromatic, acyclic,or cyclic.

In embodiments of the present technology where any of R₁ to R₆ areselected from group (b), the substituted hydrocarbyl groups of group (b)can have one or more substituents selected from hydroxyl (—OH), alkoxy,aryloxy, carbonate ester, carbamate, sulfonate, phosphinate, phosphite,phosphate, phosphonate, or combinations thereof. In some suchembodiments, the alkoxy or aryloxy substituents have the general formula—OR, where R is a hydrocarbyl group having from about 1 to about 4carbon atoms.

In actual production, amines from which the quaternary ammonium sitescan be formed are sometimes themselves mixtures in which the Rsubstituents on each amine molecule can be similar, but not identical.For example, amines derived from vegetable oil fatty acids are normallymixtures. Each of the R substituents in the amines in these mixturesconforms to the above descriptions for R₁-R₆. These amine mixtures maybe very complex. The theoretical number of possible combinations ofamine pairs grows very rapidly as the number of kinds of amines exceedsabout three, and becomes very large as the number of kinds of differentamines exceeds about five. The actual product distribution function forthe possible combinations is a statistical mixture which reflects thepopulations of the various amine components, but also reflects therelative reactivities of the different components. In at least onerandom GQ composition of the presently described technology, each GQmolecule is formed by a pair of amine molecules, the same kind ordifferent, randomly met. While not strictly accurate, such a compositionis called random for the purposes of this disclosure.

In the formula provided above for a general structure of a bis-quatmolecule of the present technology, R₇ can be a member selected fromhydrocarbyl groups having from about 2 to about 30 carbon atoms, orsubstituted hydrocarbyl groups having from about 2 to about 30 carbonatoms. For example, in some embodiments of the present technology, R₇comprises hydrocarbyl groups having from about 3 to about 8 carbon atomsor substituted hydrocarbyl groups having from about 3 to about 8 carbonatoms. In preferred embodiments of this type, R₇ has a linearconfiguration. As another example, in some embodiments of the presenttechnology, R₇ comprises hydrocarbyl groups having from about 9 to about21 carbon atoms or substituted hydrocarbyl groups having from about 9 toabout 21 carbon atoms. In preferred embodiments of this type, R₇ has aconfiguration comprising a ring structure.

In embodiments of the present technology where any of R₇ is asubstituted hydrocarbyl group, the hydrocarbyl group can have one ormore substituents selected from hydroxyl, alkoxy, aryloxy, estercarbonate, carbamate, sulfonic acid, sulfonate, phosphinic acid,phosphinate, phosphorous acid, phosphite, phosphoric acid, phosphate,phosphonate or combinations thereof. In some such embodiments, thealkoxy or aryloxy substituents have the general formula —OR, where R isa hydrocarbyl group having from about 1 to about 4 carbon atoms.

There are several characteristic that can be preferred for R₇ as used inthe present technology. For example, in at least some particularlypreferred embodiments, R₇ is hydrophilic. As another example, in atleast some embodiments, R₇ is a substituted hydrocarbyl group that isnot a hydroxyalkylene.

In various embodiments of the present technology, R₇ can be derived fromvarious sources. For example R₇ can be derived from a di-sulfonic acidester of a primary diol, a secondary diol, a derivative thereof, or acombination thereof. As another example, R₇ can be derived from anepihalohydrin. Further, R₇ can be derived from a bis-glycidyl ether. Inat least some embodiments, R₇ can be derived from a di-haloalkylhydrocarbon containing from about 2 to about 12 carbon atoms in whichthe two halogen atoms are attached to different primary or secondarysaturated carbon atoms. In some such embodiments, the di-haloalkylhydrocarbon can be substituted with one or more additional hydroxy,alkoxy, or aryloxy substituents, and preferably the additionalsubstituents are not attached to one of the halogen-bearing carbonatoms. In some preferred embodiments, the di-haloalkyl hydrocarbon isselected from dichloroethane, 1,3-dichloro-2-propanol,1,4-dibromobutane, di-(chloromethyl)benzenes, or derivatives thereof.

The anion groups A₁ and A₂ in the above formula are selectedindependently and can be:

-   -   1) negatively charged inorganic ions;    -   2) organic molecules with negatively charged functional        group(s), which can be, but are not limited to, carboxylate,        sulfonate or phosphate; or    -   3) negatively charged functional group(s) which are part of R₁,        R₂, R₃, R₄, R₅, R₆ or R₇, which can be, but are not limited to,        carboxylate, sulfonate or phosphate.

In accordance with at least some embodiments of the presently describedtechnology, at least a portion of the hydrophobes in the GQ molecule,preferably at least a portion of the hydrophobes in R₁-R₆ of the aboveformula is derived from a carboxylic acid. In at least one preferredembodiment, at least one of R₁ or R₆ is derived from a carboxylic acid.Carboxylic acids suitable for use with the present technology preferablyhave from about 13 to about 40 carbon atoms, and more preferably havefrom about 16 to about 22 carbon atoms.

In at least one preferred embodiment, the carboxylic acid is derivedfrom a fatty acid, such as an animal or vegetable oil. Carboxylic acidsderived from fatty acids typically contain from about 8 to about 24carbon atoms.

Carboxylic acids (and their derivatives, including but not limited toesters, carboxamides, carboxamidines, anhydrides, acyl chlorides andnitriles) may also be derived from other sources. Carboxylic acids fromother sources offer a wider variety of structures than do those found incommon fatty acids (mostly linear chains), such as cyclic, aromatic, andpolyfunctional compounds. Non-fatty acid derived carboxylic acids may beused with the present technology when their structural features impartuseful properties to the viscoelastic compositions.

Preferably, at least one hydrophobe is covalently bonded to asubstituent on the cationic nitrogen atom through either an ester,carboxamide, or carboxamidine functional group. Hydrophobes may also bebonded to the linker fragments of the GQ molecules through ester,carboxamide, or carboxamidine functional groups. Not being bound by anytheory, it is believed that surfactants in which the hydrophobes areattached through these functional groups are biodegraded more easilythan those in which the hydrophobes are attached as hydrocarbylfunctional groups.

One readily accessible method for preparing GQs is by substitutionreactions between m moles of a substrate and 2 m moles of a tertiaryamine (having a theoretical functionality of 1), where “m” is a numberused herein to illustrate the ratio of moles of substrate to moles oftertiary amine, and where the substrate has 2 m equivalents offunctional groups (leaving groups) that may become a nucleofuge insubstitution reactions. The net theoretical functionality of the productis zero, since the 2 m moles of tertiary amines react at the 2 mequivalents of sites with leaving groups. The formation of a fourth bondto the amine nitrogen quaternizes the tertiary amine, and thus generatesa cationic site.

Any molecule that has two suitable leaving groups can serve as asubstrate to form the linker fragment in a GQ molecule. Preferredsubstrates are those in which the linker derived from the substrateseparates the two cationic nitrogen atoms by from about 2 to about 12atoms. Suitable substrates may contain other functional groups, such ashydroxyl groups, so long as they do not block the reaction between theamine and the substrate. Functional groups may also become attached tothe linker fragment by additional chemical reactions subsequent to thequaternization reactions.

FIG. 2 illustrates such a method. In FIG. 2, the substrate molecule hastwo leaving groups, X and Y, and provides two sites that can react withtwo amine molecules. As nucleofuges in the substitution reaction, one orboth of X and Y may become Anion, (A₁) or Anion₂ (A₂) for the resultingGQ molecule, but not necessarily. X and Y may themselves react furtherafter the initial substitution reactions. For example, an alkoxidenucleofuge may be converted to a carboxylate anion by reaction with anacid anhydride. FIG. 2 also shows that the resulting GQ can be modifiedthrough a subsequent reaction with [Z], which contains a functionalgroup Z that can be bonded to the GQ, to make the modified GQ.

Examples of readily accessible substrates that may form the linkerfragments through substitution reactions include, but are not limitedto:

-   -   di-haloalkyl hydrocarbons (cyclic or acyclic, aliphatic or        aromatic) containing from about 2 to about 18 carbon atoms in        which the two halogen atoms are attached to different primary or        secondary saturated carbon atoms;    -   substituted di-haloalkyl hydrocarbons (cyclic or acyclic,        aliphatic or aromatic) containing from about 2 to about 18        carbon atoms in which the two halogen atoms are attached to        different primary or secondary saturated carbon atoms, and in        which the hydrocarbon is additionally substituted with hydroxyl        (—OH); or, alkoxy and aryloxy (—OR, where R is a hydrocarbyl        group having from about 1 to about 24 carbon atoms), so long as        the additional substituents are not attached to one of the        halogen-bearing carbon atoms;    -   di-sulfonic acid esters of primary diols, secondary diols, or a        combination thereof,    -   epihalohydrins, or    -   bis-glycidyl ethers

Solvents are not necessary to prepare random GQ compositions of thepresently described technology. However, random GQ compositions arepreferably prepared in solvents to aid in processing and handling.Examples of solvents that can be used in the present technology include,for example, methanol, ethanol, 2-propanol, 1-propanol, 2-butanone,acetone, glycol ethers and water. In general, organic solvents with atleast partial water solubility are suitable so long as they do notinterfere with the chemical reactions involved in making the bis-quatsor GQs. Many of the bis-quats solidify when being cooled to around roomtemperature, so solvents are usually preferred to facilitate handling.

Generally, when making random GQs, the amine (preferably a tertiaryamidoamine) or amine mixture can be dissolved in a water compatiblesolvent. Water can be used as a co-solvent at levels from about 1% toabout 99% by weight of the solvent composition.

Then, if an epihalohydrin substrate is used, acid can be added slowly tothe solution in sufficient quantity to react with half of the tertiaryamine equivalents. Once partial neutralization of the amine iscompleted, the substrate (e.g., epichlorohydrin) can be added to thesolution slowly, typically over a period of from approximately 15minutes to about 2 hours. The temperature during the addition of thesubstrate is preferably from about 25° C. to about 100° C., and morepreferably from about 40° C. to about 70° C. The total charge ofsubstrate is preferably from about 0.5 to about 0.6 moles per mole oftertiary amine. Preferably, a slight excess of the substrate, forexample about 0.52 moles per mole of tertiary amine, is used to achievesufficient quaternization such that low levels of free amine and aminesalt are present in the final product.

After the substrate charge is complete, the process is continued untilreaction of the substrate is complete. Reaction degree of completion maybe determined by titration methods, for example by titration of residualfree amine and amine salt levels, and by titration for halide content bysilver nitrate methods. If necessary, additional substrate is charged toreduce levels of free amine and amine salt to acceptably low levels.Acceptably low levels are preferably such that at least about 90% of thetotal initial tertiary amine equivalents charged are converted toquaternary ammonium compounds (about 90% molar conversion). Once thereaction is complete, properties such as actives concentration and pHare adjusted (if desired) through the addition of additional solvents(for actives) and acids or bases (for pH adjustment).

Some bis-quats of the present technology can be used as the activeingredients in gellant compositions. Addition of undiluted solid gellantcompositions to water frequently causes the solids to become coated withgel, and dissolution becomes difficult and may require additionalheating, mixing and time. Formulation of the bis-quats or GQs of thepresent technology with organic solvents, or mixtures of organicsolvents and water is preferred, because it provides liquid compositionsthat dissolve efficiently when added to a solution to be gelled orthickened. In instances where minimal organic solvents are desired, suchas in high actives solid gellants, mechanical dissolution techniques,such as high-shear mixers, can be used to prepare gellant solutions.

The following specific reaction schemes further demonstrate methods forpreparing random bis-quaternary compounds of the present technology.

Reaction Scheme 1:

In this scheme, the linker is derived from 1,2-dichloroethane. Thetertiary amine is the stearamidopropyldimethylamine (SAPDMA) derivedfrom stearic acid and 3-dimethylaminopropyl-1-amine. The chlorine atomsare nucleofuges, which become the negative counter ions (chloride) thatmaintain a net electrical charge of zero (charge balance). The productis a gemini stearamidopropyl gemini quat.

A common practice in the literature regarding gemini surfactants is touse a condensed notation to describe both the hydrophobe and the linker(also referred to as “spacer”). In general, the notation used is m-n-m,where m is the length of the hydrophobe carbon chain in the alkylamine,and n is the number of carbon atoms in the linker. Modifications to thisnotation are used in this disclosure to describe polycationic quats.Some designation is required to note that the hydrophobes on thebis-quats in Scheme 1 are not from alkylamines, but instead they arefrom amidopropyldimethylamines (APDMA). The notation used hereafter forthis type of GQ is 18APDMA-2-18APDMA. This notation example specifiesthat both hydrophobes have 18 carbon atoms which are part of anamidopropyldimethylamines, and that the linker is a 2 carbon atom chain(ethylene).

Reaction Scheme 2:

In this scheme, epichlorohydrin is used to form the linker. One mole ofacid, hydrochloric acid reacts with one mole of the tertiary amine. Theepichlorohydrin reacts with the amine hydrochloride salt (through theoxirane functional group) and the free tertiary amine (through thechloromethyl group) to form the GQ. The GQ in this case may berepresented by the notation 18APDMA-3(OH)-18APDMA. The linker in thiscase has 3 carbon atoms, but also includes a hydroxyl group, which isindicated by the (OH). As in Scheme 1, the negative counter ions arechloride.

Reaction Scheme 3:

Like in Reaction Scheme 2, this scheme uses two moles of tertiary aminewith one mole of an acid, and the linker is derived fromepichlorohydrin. However, in this reaction scheme, the acid ispara-toluenesulfonic acid (PTSA). The result of this aspect of ReactionScheme 3 is that half of the negative counter ions for this GQ are thetoluenesulfonate anion, while the other half required to achieve chargebalance is chloride. Organic sulfonate counter ions, especially aromaticones, are desirable in some cases because they impart useful propertiesto the compositions of the present technology e.g., they promote vesicleformation.

The notation for this GQ also differs from that in Reaction Scheme 2,because the hydrophobe is oleyl in this case instead of stearyl (C₁₇H₃₃instead of C₁₇H₃₅). The presence of double bonds in fatty acids andtheir derivatives is commonly notated by the number of carbon atoms inthe fatty acid followed by a colon followed by the number of doublebonds in the molecule. Thus oleic acid may be notated by 18:1. Applyingthis notation to the GQ notation described earlier, the GQ from Scheme 3becomes 18:1APDMA-3(OH)-18:1APDMA. The counter ions in the GQ are notspecified in the shortened notation.

Reaction Scheme 4:

This reaction scheme uses a diglycidyl compound to form the linker.

In this scheme, the diglycidyl compound is resorcinol diglycidyl ether(RDGE). For reactions of amines with diglycidyl linkers, the amines arefirst fully neutralized with an acid (typically hydrochloric, PTSA orxylene sulfonic acid). The amine salt then reacts with the oxiranefunctionalities of the diglycidyl compound to form the GQ. When usingthe shortened notation for GQs from diglycidyl compounds, anabbreviation for the diglycidyl compound is used, i.e.,18APDMA-RDGE-18APDMA for this GQ (no indication is used for the twohydroxyls in this case).

Note that this scheme may be used to produce compounds free from halidesalts by the use of sulfonic acid to neutralize the amines. Otherdiglycidyl ethers (DGE), such as triethyleneglycol DGE, butanediol DGEand bisphenol DGE may also be used.

Reaction Scheme 5:

Reaction Scheme 5 uses a mixture of different amidoamines to make arandom mixture of GQs. In this case, two different kinds of amidoamines(stearyl=18 and oleyl=18:1) are used in equimolar amounts. When amixture of amines is used, the product composition is a statisticalmixture determined by the relative reactivities and concentrations ofthe different amines. Any number of different amidoamines may be used,so long as the total moles of tertiary amine are sufficient to reactwith 1 mole of the substrate (epichlorohydrin in this scheme).

The product mixture of this example contains 18APDMA-3(OH)-18APDMA,18:1APDMA-3(OH)-18APDMA, and 18:1APDMA-3(OH)-18:1APDMA.

Reaction Scheme 6:

In this scheme, an amidoamine(stearamidopropyldimethylamine) is usedwith a bis-hydroxyethyl-alkylamine to make a GQ composition with1,3-dichloro-2-propanol as the substrate to provide the linker in theGQ. As discussed above, when a mixture of amines is used, the productcomposition is a statistical mixture determined by the relativereactivities and concentrations of the different amines, which is calleda random GQ composition in the present technology. Any number ofdifferent amidoamines and alkylamines may be used, so long as the totalmoles of tertiary amine are sufficient to react with 1 mole of thelinker.

The linker in this case (2-hydroxypropyl) is the same as that derivedfrom using epichlorohydrin as a substrate. For shortened notation, thehydroxyethyl group is abbreviated by HE with a subscript 2 because thereare two of them. This mixture consists of 18APDMA-3(OH)-18HE₂,18HE₂-3(OH)-18HE₂, and 18APDMA-3(OH)-18APDMA.

Reaction Scheme 7:

This reaction scheme shows a method for preparing a random GQcomposition from an amidoamine(stearamidopropyldimethylamine) and anester amine, using epichlorohydrin as the substrate. Shortened notationfor ester amines is EA, with a subscript to indicate the number ofhydrophobe substituents on the nitrogen that have ester bonds. Thus,18EA₁-3(OH)-18EA, is the third GQ shown in Reaction Scheme 7 in whichboth quaternary nitrogens have hydrophobe substituents with ester bonds.

Reaction Scheme 8:

As shown in Reaction Scheme 8, a GQ composition is prepared from thesubstrate 1,2-dichloroethane and a carboxamidine,1-hydroxyethyl-2-heptadecenyl-2-imidazoline.

Reaction Scheme 9:

In this scheme, a non-fatty acid carboxylic acid derivative is used toprepare a GQ composition. As in Reaction Scheme 2, two moles of a fattyacid derived amidopropyldimethylamines are provided as the tertiaryamines and the linker is derived from epichlorohydrin. However, thisbis-quat is not prepared using HCl, but instead using a dicarboxylicacid derivative, ortho-phthalic anhydride. The nucleofuges from theepichlorohydrin in this case may be formally considered to be oneequivalent of chloride and one equivalent of alkoxide anion (derivedfrom the ring opening of the oxirane). The alkoxide anion is “trapped”by subsequent reaction with the ortho-phthalic anhydride to form thephthalate half-ester. The carboxylate anion also formed during thisprocess provides one equivalent of negatively charged counter ion to thecationic nitrogens. The additional equivalent of counter ion comes fromthe chloride equivalent. Compounds such as these, in which at least aportion of the counter ion is also covalently bound to the cationicmolecule, provide certain desired performance effects in theircompositions, such as increased water solubility, or improvedviscoelastic, gellant, thickening or drag reducing properties.

Dissymmetric or Structurally Defined Bis-quats

In accordance with at least some embodiments, the presently describedtechnology provides structurally defined bis-quats, which can be, forexample, dissymmetric GQs or dissymmetric non-gemini bis-quats.

As used herein, a bis-quat composition is described as “structurallydefined” if the distribution of the symmetric components in thepolycationic composition is different from the distribution that wouldotherwise be obtained by the random process as described above. As usedherein, “distribution of the symmetric components” means the pairingsbetween NR₁R₂R₃ and NR₄R₅R₆.

Structurally defined bis-quats of the present technology can be formedthrough what can be called a stepwise process. Important points of thestepwise process include that at least two different kinds of amines oftheoretical functionality 1 are used to provide two equivalents ofamines that can react with one mole of a substrate of theoreticalfunctionality 2, and also that the chemical reactions that form thebis-quats are conducted in such a way that dissymmetry or a substantialdegree of structural definition in the product molecules is established.FIG. 3 schematically illustrates such a dissymmetric arrangement.

Each of the cationic fragments as shown in FIG. 3 can be derived from amixture of different amines. Therefore two mixtures of different aminescan be used for each of the cationic fragments. In accordance with atleast one embodiment of the present technology, the compositions of thetwo mixtures must be different (different in chemical composition, inconcentrations of like components, or both).

When mixtures of amines are derived from naturally occurring oils(vegetable or animal), then many of the fatty acid components areidentical (although they may present in different amounts). If the twoamine mixtures used for cationic fragments 1 and 2 of FIG. 3 differ onlyin the source of their fatty acid derived hydrophobes, then it is likelythat a stepwise process for preparing polycationic quats will producesome polycationic components which are not dissymmetric. However, thedistribution of the different fatty acids is relatively unique for eachsource. For example, fatty acids derived from soybean oil typicallyinclude about 7 different fatty acids. Corn oil fatty acids typicallyinclude about 5 different fatty acids, all of which are found in soyafatty acids, but in different proportions. Therefore, if cationicfragment 1 is soya derived, while cationic fragment 2 is corn derived,then the bis-quat composition from the two will contain symmetriccomponents. However, the proportions of both symmetric and dissymmetricbis-quat components formed by the stepwise process are different fromthe proportions that are obtained when the stepwise process of thepresently described technology is not used. When the amines are mixedbefore quaternization, in a process as described above for random GQcomposition, a statistical mixture determined by the relativereactivities and concentrations of the different amines will result.

A person of ordinary skill in the art will also understand that while areaction may be substantially selective for a certain leaving group overanother, it is not necessary for it to be 100% selective for thepurposes of the present technology. Thus, even when the amine mixturesused in the stepwise process have no common components, it is possiblethat some amounts of symmetric polycationic compounds are formed.Therefore, for purpose of the presently described technology, abis-cationic composition is described as structurally defined if thedistribution of the symmetric components in the polycationic compositionis different from the distribution that would otherwise be obtained by arandom process.

Preferably, the two amine mixtures are selected such that they havesignificant distinguishing features, such as alkoxylated amines withdimethyl substituted amines, or the fatty acid derived hydrophobes havedistinguishing features such as degree of saturation and amounts ofcarbon chain lengths of about 18 and higher. The stepwise process canenhance the amounts of dissymmetric polycationic quats over what wouldbe obtained by the random process as described above.

In accordance with the presently described technology, the structuraldefinition of the polycationic compositions is typically apparentthrough its effect on physical properties of the viscoelasticcompositions such as tendency to crystallize, melting point, solubilityin water and other solvents, and in the rheological properties impartedto their solutions. Some or all of the properties of a structurallydefined polycationic composition normally are different from anon-structurally defined polycationic composition made from the samecomponents by a random process.

Similar to that for a bis-quat molecule in a random composition, thestructure of dissymmetric bis-quat molecules in one or more structurallydefined bis-quat compositions of the presently described technology canbe represented by the following general formula:

In some embodiments of dissymmetric bis-quat molecules of the presenttechnology having this general structure, R₂, R₃, R₄, and R₅ can bemembers independently selected from (a) hydrocarbyl groups having fromabout 1 to about 4 carbon atoms, or (b) substituted hydrocarbyl groupshaving from about 1 to about 4 carbon atoms. Alternatively, R₂ and R₃can be members of a heterocyclic ring, preferably a heterocyclic ringcontaining 5 or 6 carbon atoms. In such embodiments, R₄ and R₅ can bemembers of a different heterocyclic ring, or can be independentlyselected from group (a) as defined above or group (b) as defined above.When R₄ and R₅ are members of a different heterocyclic ring, that ringpreferably contains 5 or 6 carbon atoms.

Additionally, in some embodiments of such dissymmetric bis-quatmolecules of the present technology, R₁ and R₆ can be membersindependently selected from group (a) as defined above, group (b) asdefined above, or (c) hydrocarbyl groups having from about 13 to about40 carbon atoms or substituted hydrocarbyl groups having from about 13to about 40 carbon atoms. In some such embodiments, the hydrocarbylgroups or substituted hydrocarbyl groups of group (c) can comprisecarboxamides, carboximides, polycarboxamides, polycarboximides,carboxamidines, carboximidines, carboxylic esters, polycarboxylicesters, carboxylic acids, polycarboxylic acids, carboxylates,polycarboxylates, or combinations thereof.

In some particularly preferred embodiments, at least one of R₁ or R₆ isa member of group (c), and in some such embodiments, can furthercomprise a cyclo hydrocarbyl ring or a heterocyclic ring. In someembodiments, R₁ and R₆ are both chosen from group (c), while in others,only R₁ or R₆ is chosen from group (c). In at least one embodiment, R₁is selected from group (c) and R₆ is selected from group (a) or group(b). In at last one embodiment, each of R₄, R₅, and R₆ is a hydrocarbylgroup having from about 1 to about 4 carbon atoms or a substitutedhydrocarbyl groups having from about 1 to about 4 carbon atoms. In somepreferred embodiments, at least one of R₁ or R₆ is derived from acarboxylic acid having from about 13 to about 40 carbon atoms, and morepreferably from about 16 to about 22 carbon atoms. In some particularlypreferred embodiments, the carboxylic acid is derived from an animal orvegetable oil.

Moreover, in embodiments of dissymmetric bis-quat molecules of thepresent technology, at least one of R₁, R₂, or R₃ is different from eachof R₄, R₅ and R₆.

It should be appreciated that the hydrocarbyl groups of groups (a), (b)and (c) can be arranged in any chemically rational combination,including aliphatic, aromatic, acyclic or cyclic.

In embodiments of the present technology where any of R₁ to R₆ areselected from group (b), the substituted hydrocarbyl groups of group (b)can have one or more substituents selected from hydroxyl (—OH), alkoxy,aryloxy, carbonate ester, carbamate, sulfonate, phosphinate, phosphite,phosphate, phosphonate, or combinations thereof. In some suchembodiments, the alkoxy or aryloxy substituents have the general formula—OR, where R is a hydrocarbyl group having from about 1 to about 4carbon atoms.

In the formula provided above for a general structure of a dissymmetricbis-quat molecules of the present technology, R₇ can be a memberselected from the group consisting of hydrocarbyl groups having fromabout 2 to about 30 carbon atoms, and substituted hydrocarbyl groupshaving from about 2 to about 30 carbon atoms. For example, in someembodiments of the present technology, R₇ comprises hydrocarbyl groupshaving from about 3 to about 8 carbon atoms or substituted hydrocarbylgroups having from about 3 to about 8 carbon atoms. In preferredembodiments of this type, R₇ has a linear configuration. As anotherexample, in some embodiments of the present technology, R₇ compriseshydrocarbyl groups having from about 9 to about 21 carbon atoms orsubstituted hydrocarbyl groups having from about 9 to about 21 carbonatoms. In preferred embodiments of this type, R₇ has a configurationcomprising a ring structure. In yet another preferred embodiment, R₇comprises a substituted aromatic ring or rings.

In embodiments of the present technology where any of R₇ is asubstituted hydrocarbyl group, the hydrocarbyl group can have one ormore substituents selected from hydroxyl, alkoxy, aryloxy, estercarbonate, carbamate, sulfonic acid, sulfonate, phosphinic acid,phosphinate, phosphorous acid, phosphite, phosphoric acid, phosphate,phosphonate or combinations thereof. In some such embodiments, thealkoxy or aryloxy substituents have the general formula —OR, where R isa hydrocarbyl group having from about 1 to about 4 carbon atoms.

There are several characteristic that can be preferred for R₇ as used inthe present technology. For example, in at least some particularlypreferred embodiments, R₇ is hydrophilic. As another example, in someembodiments, R₇ is a substituted aromatic group. As yet another example,in at least some embodiments, R₇ is a substituted hydrocarbyl group thatis not a hydroxyalkylene.

In different embodiments of the present technology, R₇ can be derivedfrom various sources. For example, in some preferred embodiments, R₇ isderived from a substrate including two reactive sites with differentreactivities. As another example, R₇ can be derived from a di-sulfonicacid ester of a primary diol, a secondary diol, a derivative thereof, ora combination thereof. As another example, R₇ can be derived from anepihalohydrin. Further, R₇ can be derived from a bis-glycidyl ether. Inat least some embodiments, R₇ can be derived from a di-haloalkylhydrocarbon containing from about 2 to about 12 carbon atoms in whichthe two halogen atoms are attached to different primary or secondarysaturated carbon atoms, and wherein the two halogen atoms have differentreactivities. In some such embodiments, the two halogen atoms aredifferent. In some embodiments, the di-haloalkyl hydrocarbon can besubstituted with one or more additional hydroxy, alkoxy, or aryloxysubstituents, and the additional substituents are not attached to one ofthe halogen-bearing carbon atoms. Further, the di-haloalkyl hydrocarboncan have a primary bromoalkyl group and a secondary chloroalkyl group.

The anion groups A₁ and A₂ in the above formula are selectedindependently and can be:

1) negatively charged inorganic ions;

2) organic molecules with negatively charged functional group(s), whichcan be, but are not limited to, carboxylate, sulfonate or phosphate; or

3) negatively charged functional group(s) which are part of R₁, R₂, R₃,R₄, R₅, R₆ or R₇, which can be, but are not limited to, carboxylate,sulfonate or phosphate.

When there is one or more hydrophobe carbon chains attached to eachquaternary nitrogen atom in the above formula, the bis-quat is agemini-quat (GQ). When there is only one hydrophobe chain per twoquaternary nitrogen atoms, the bis-quat is a non-gemini bis-quat. It hasbeen surprisingly found that non-gemini bis-quats of the presenttechnology having one hydrophobe on one quaternary nitrogen atom and nohydrophobe on the other quaternary nitrogen atom exhibit someparticularly useful and unexpected properties. For example, thesebis-quats have the ability to form viscoelastic gels over a broad rangeof salt concentrations (e.g. from about 5% by weight to about 75% byweight salt). Salt solutions (brines) with salt concentrations aboveabout 20% by weight have densities substantially higher than that ofwater, and are used in well bore service fluids for the advantages thehigher density or salt concentrations confer.

Some compositions and formulation techniques for solids-free brinesolutions for use in well bore service fluids are taught in Completionand Workover Fluids, by Kenneth L. Bridges, SPE Monograph Volume 19(Society of Petroleum Engineers, Richardson, Tex., 2000), the content ofwhich is incorporated herein by reference. Such brine solutions can beformulated to a range of densities, from about 9.7 to about 22.5 poundsper gallon, for use in aqueous completion fluids where their higherdensity relative to water is advantageous. For example, in the wellcompletion process, a transition from a drilling or stimulation processis made as the well bore is prepared to produce hydrocarbons. Thecompletion fluid serves to control formation pressures, and may alsoprovide protection against or removal of formation damage.

Examples of brine solutions that can be suitable for use with thepresent technology can contain one type of salt, or can containcombinations or mixtures of salts. For example, some brine solutionscontain water and up to about 25% or about 26% by weight sodiumchloride, up to about 24% by weight potassium chloride, up to about 47%by weight sodium bromide, up to about 40% by weight calcium chloride, orup to about 66% by weight calcium bromide. Some other examples of brinesolutions contain combinations or mixtures of two or more salts. Brinesolutions containing zinc bromide, for example, preferably also containat least one or two other salts, such as calcium bromide and/or calciumchloride. One example brine containing zinc bromide for use in acompletion fluid is a composition containing about 52.8% by weight zincbromide (ZnBr₂), about 22.8% calcium bromide (CaBr₂), and about 24.4%water, with the resultant solution having a density of about 19.2 lb.per gallon at about 60° C.

Thickening or gellation of brine solutions can impart additionaladvantages, such as reduced fluid leak off into the formation and lessformation damage. Particularly preferred embodiments of non-geminibis-quats of the present technology can thicken brine solutions and formviscoelastic gels at levels of from about 3% by weight to about 10% byweight bis-quat by weight of the composition.

In the present technology, structural definition can be established by astepwise process, in which, in the first step, one equivalent of atertiary amine (or a mixture of tertiary amines) is reacted selectivelyat one reactive site on the substrate. This creates an intermediatecationic quaternary ammonium compound in which the quaternary nitrogenatom bears a substituent which has a nucleofuge, so that a subsequentsubstitution reaction may then be effected with a second equivalent of adifferent tertiary amine (or a different mixture of tertiary amines). Atthe conclusion of the second step, the composition contains bis-quats,which are structurally defined in that, for at least a preponderance ofthe molecules, each molecule contains one cationic nitrogen derived fromthe first step (first equivalent of tertiary amine(s)) and one cationicnitrogen atom derived from the second step (second equivalent oftertiary amine(s)). To effect this stepwise process, it is necessary toachieve substantial selectivity between the reactions with the twoleaving groups on the substrate.

The substrate to provide the linker fragment of the dissymmetricbis-quaternary ammonium compound of the present technology can bedesignated by the following structure:

X and Y represent atoms or functional groups of atoms attached to thereactive carbon atoms on the substrate. The carbon atoms are reactive inthat X and Y are suitable nucleofuges in substitution reactions withtertiary amines. Furthermore, the reactive sites on the substrate arereactive to different degrees under suitable conditions, so that asubstitution reaction may happen at one site while leaving the otherreactive site substantially intact.

For example, X and Y may be different pairs of halogen atoms, especiallychlorine and bromine, or chlorine and iodine. Chloroalkyl groups aregenerally less reactive than either bromoalkyl or iodoalkyl groups insubstitution reactions, when the alkyl groups are the same. By carefullycontrolling reaction conditions to minimize reaction at the reactivesite bearing a chlorine atom, selective reaction at a reactive sitebearing either a bromine or an iodine atom may be effected in the firststep as described above. In the second step, additional amine can bereacted with the chloroalkyl group under conditions sufficient to effectthat reaction, thus generating the structurally defined bis-quats.

Other factors can also enhance the reaction selectivity between thereactive sites on the substrate. For example, a primary carbon isgenerally more susceptible to substitution reactions than a secondarycarbon atom because of steric hindrance. A primary bromoalkyl reactivesite is generally more reactive than a secondary bromoalkyl group, whichis generally more reactive than a secondary chloroalkyl group (which isless reactive than a primary chloroalkyl group). Thus, a primarybromoalkyl group can be reacted with greater selectivity in the presenceof a secondary rather than primary chloroalkyl group. Additional factorsthat affect the reactivities of substrates in substitution reaction aredescribed more thoroughly in Chapter 10 of the fifth edition of March'sAdvanced Organic Chemistry, by Michael B. Smith and Jerry March (2001),which is incorporated herein by reference. Within that chapter, leavinggroups are ranked by their ability to become a nucleofuge insubstitution reactions at saturated carbon atoms. Suitable pairs of Xand Y may be selected from those rankings such that suitable reactionselectivity is attained. To achieve the dissymmetric bis-quats describedhere, it is sufficient that the X and Y groups are attached to reactivesites which may be reacted first at a preponderance of one site followedby a second reaction at the remainder of the sites.

One category of preferred substrates in this process is epihalohydrins.In an epihalohydrin, X and Y are a chloromethyl group and an oxiranefunctional group. As illustrated in FIG. 4, substantially selectivereaction with the oxirane functionality can be effected. In FIG. 4,first, a first equivalent of tertiary amine(s) is neutralized with anacid so that only tertiary hydrogen ammonium salts are present. Theseammonium salts are then reacted with the epihalohydrins through theoxirane functionality. Because, essentially, no free amine is present,little or no reaction occurs at the halomethyl functional group. Oncethe reaction between the oxirane and ammonium salts is completed, thesecond equivalent of different tertiary amine(s) is reacted with thecomposition resulting from the first step. The free amine reacts withthe halomethyl functional groups in this step, thus establishing thestructural definition described earlier.

In FIG. 4, X can be a chlorine, bromine or iodine atom. HA is aneutralizing acid and A⁻ is the conjugate base of the acid.Non-exhaustive examples of suitable acids include hydrogen halides ortheir aqueous solutions; inorganic oxo acids, such as nitric acid;alkylsulfonic acids, such as methanesulfonic acid and alpha olefinsulfonic acids; alkylarylsulfonic acids such as toluenesulfonic acid,xylenesulfonic acid, and dodecylbenzenesulfonic acid; andarylakylsulfonic acids.

For example, in order to make a dissymmetric or structurally definedbis-quat using an epihalohydrin as the substrate, the first tertiaryamine (or amine mixture), preferably a tertiary amidoamine, is firstdissolved in a water compatible solvent. Water is used as a co-solventat levels from about 1% to about 99% by weight of the solventcomposition. Acid can then be added slowly to the solution in sufficientquantity to react with all of the first tertiary amine. Onceneutralization of the amine is completed, epihalohydrin can be added tothe solution slowly, typically from about 15 minutes to about 2 hours.The temperature during the addition of the epihalohydrin is preferablyfrom about 25 to about 100° C. The total charge of epihalohydrin ispreferably from about 1.0 to about 1.2 moles per mole of the firsttertiary amine. Preferably, a slight excess of epihalohydrin, such asabout 1.03 moles per mole of first tertiary amine, is used to effectmore complete quaternization so that low levels of free amine and aminesalt are present in the final product.

After the epihalohydrin charge is complete, the process can be continueduntil reaction of the first amine is complete. Reaction degree ofcompletion for the first amine may be determined by titration methods,for example by titration for residual free amine and amine salt levels.If necessary, additional epihalohydrin is charged to reduce levels offree amine and amine salt to acceptable levels. Acceptable levels forthe first step are preferably such that at least about 90% of the totalamine equivalents charged are converted to quaternary ammonium compounds(about 90% molar conversion). Once reaction of the first amine issufficient, a second amine (preferably different from the first amine)is slowly charged to the solution from step 1, preferably over fromabout 15 minutes to about 4 hours. The amount of second amine charged isabout one mole per mole of epihalohydrin. The temperature during theaddition of the second amine is preferably from about 25° C. to about100° C. Again, the process is continued until degree of reaction, asdetermined by titration methods, is acceptable. If necessary, additionalepihalohydrin may be charged to achieve an acceptable level of reactantconversion, such as about 90% molar conversion minimum to quaternaryammonium compounds. Once the degree of conversion is acceptable,properties such as actives concentration and pH can be adjusted (ifdesired) through the addition of additional solvents (for actives) andacids or bases (for pH adjustment).

The following reaction schemes provide more specific illustrations ofthe stepwise process and the structurally defined compositions of thepresently described technology.

Reaction Scheme 10:

Reaction Scheme 10 uses the same components in the same ratios as thosein Reaction Scheme 5 described above. Unlike Reaction Scheme 5, whichproduces a statistical mixture (i.e., a random GQ composition)determined by the relative reactivities and concentrations of thedifferent amines, Reaction Scheme 10 produces structurally defined GQcomposition containing a much higher amount of the dissymmetric18APDMA-3(OH)-18:1 APDMA, and much less of 18:1APDMA-3 (OH)-18:1APDMAand 18APDMA-3 (OH)-18APDMA.

Such a structurally defined composition is often preferred, becausewhile the 18APDMA component can provide superior viscoelasticity andhigher viscosity over the 18:1 APDMA, 18APDMA-3(OH)-18APDMA is a solidat about 42 wt % active ingredients in a mixture of water and2-propanol, and it is more difficult to handle for making viscoelasticsolutions or gels. Furthermore, 18APDMA-3(OH)-18APDMA based viscoelasticsolutions tend to become hazy to opaque around room temperature, becauseof the tendency of the saturated C18 hydrophobe to cause the bis-quat tocrystallize. On the other hand, 18:1 APDMA-3(OH)-18:1 APDMA is a softpaste at about 50 wt % active ingredients in water and 2-propanol, so itis easier to handle for making viscoelastic solutions or gels. 18:1APDMA-3(OH)-18:1 APDMA can provide clear viscoelastic gels at roomtemperature, but it does not provide viscosities as high as the18APDMA-3(OH)-18APDMA, especially at higher temperatures. Thedissymmetric 18APDMA-3(OH)-18:1APDMA bis-quat, on the other hand, is aliquid at room temperature in an about 50 wt % active ingredientsolution with 2-propanol and water. Furthermore, its viscoelasticsolutions or gels are clear to slightly hazy at room temperature andhave higher viscosity than comparable gels made from18:1APDMA-3(OH)-18:1APDMA.

A person of ordinary skill in the art will understand that commerciallyavailable stearic (C18) and oleyl (C18:1) derivatives typically containfrom about 5% to about 40% (by weight) of other fatty acid components(which were not represented in the scheme below). If the othercomponents are taken into consideration, the compositions are stillstructurally defined, with enhanced amounts of the dissymmetric18APDMA-3(OH)-18:1 APDMA bis-quat.

Reaction Scheme 11:

This reaction scheme uses the same components as those in ReactionScheme 6 described above. Scheme 11 does not give the statisticalmixture of random bis-quats produced in Scheme 6, but gives an enhancedlevel of dissymmetric bis-cationic 18APDMA-3(OH)-18HE₂, and less of thesymmetric bis-cationic 18HE₂-3(OH)-18HE₂ and 18APDMA-3(OH)-18APDMA. Thisscheme also illustrates the use of para-toluenesulfonic acid forproducing structurally defined bis-cationic compounds.

Similarly, Reaction Scheme 7 described above can also be modified to atwo step process, which would produce a structurally defined compositionwith enhanced 18EA₁-3(OH)-18APDMA.

Reaction Scheme 12:

Reaction Scheme 12 illustrates the process for preparing a structurallydefined bis-quat composition from alkylamine derivatives. The tallowamine derivative (ethoxylate) is a mixture in which the alkyl chains arethose which occur in animal tallow. For example, bovine fat tallowderived amine may contain C₁₄-C₁₈ chains, which typically containcombinations of from 0 to 3 double bonds. The other amine,erucyl-dihydroxyethylamine, is typically derived from high erucic(C22:1) rapeseed oil. Only the enhanced dissymmetric component,(14-18)HE₂-3(OH)-(22:1)HE₂, is represented in the scheme below.

Reaction Scheme 13:

Reaction Scheme 13 as shown below illustrates a particularly usefulprocess and composition for structurally defined polycationiccompositions.

The first equivalent of amines is a mixture of amidoamines derived fromhigh erucic rapeseed oil (HEAR), which has an especially highconcentration of C22:1 hydrophobe chain length, but also includesC₁₆-C₂₀ chains with from 0 to 3 double bonds. The second step uses anamine mixture derived from soybean oil (Soya), which includes C12-18:i,where i may be from 0 to 3. The resulting structurally definedcomposition is particularly desirable because it combines a componentfrom HEAR amidoamine that can give excellent theological properties toaqueous compositions when being incorporated into a bis-quat, but has ahigher cost, with a component from Soya amidoamine that has a low costand can gives moderate performance when being incorporated into abis-quat. In such a way, the properties of the structurally definedbis-quat are superior to a blend of the two separate bis-quats based oneither HEAR amidoamine or Soya amidoamine only.

Modified Polycationic Compounds

In accordance with an other embodiment, the present technology providesmodified polycationic compositions in which the polycationic moleculeshave additional chemical functional groups that, for example, may beanionic at some pH ranges. These modified polycationic compositions canbe obtained by chemical reactions subsequently performed on polycationicmolecules already formed or concurrently with the formation of thepolycationic molecules. Modified polycationic compositions having asubstantial degree of structural definition are especially desired inthe present technology.

For example, one group of the modified polycationic compounds providinguseful properties are polycationic carboxylates (“PCCs”). A PCC can beformed by acylation of a polycationic compound with a dicarboxylic acidanhydride. The polycationic compound must have a hydroxyl functionalgroup (or groups), such as the hydroxyl group formed throughquaternization tertiary amines with an epihalohydrin. The new producthas the original polycationic components plus a new ester linkage andeither a carboxylic acid or carboxylate anion functional group. Since anacid anhydride reacts with water and other hydroxylic materials, thosemust be substantially removed before starting acylation of thepolycationic compound. The free acid group generated by the acylation ispreferably neutralized, but not necessarily.

PCCs of the present technology demonstrate unexpected and usefulresults, and they can greatly reduce or completely eliminate therequirement for salts, cationic surfactants, or other additives. Use ofPCCs in viscoelastic compositions of the present technology can beparticularly desirable in applications when salts are not available, orwhen possible ground contamination with salts is not acceptable.

In at least one embodiment using a PCC of the present technology, aviscoelastic composition is provided that comprises water and aneffective amount of at least one polycationic quaternary ammoniumcompound to control the viscoelasticity of the composition, wherein theat least one polycationic quaternary ammonium compound comprises acarboxylate functional polycationic quaternary ammonium compound. In atleast one preferred embodiment, the carboxylate functional polycationicquaternary ammonium compound is produced by converting at least onealkoxide nucleofuge in a quaternary ammonium compound to a carboxylategroup with an acid anhydride.

In at least one embodiment, a polycationic carboxylate of the presenttechnology has the following general formula:

In the general structure set forth above R₇ is preferably a carboxylateanion containing from about 2 to about 24 carbon atoms. R₁ through R₆can be selected according to the descriptions set forth above for othertypes of gemini bis-quaternary compounds of the present technology. Forexample, in at least some embodiments, R₂, R₃, R₄, and R₅ can beindependently selected from: (a) hydrocarbyl groups having from about 1to about 4 carbon atoms; or (b) substituted hydrocarbyl groups havingfrom about 1 to about 4 carbon atoms. Alternatively, R₂ and R₃ can bemembers of a heterocyclic ring, and R₄ and R₅ can be members of adifferent heterocyclic ring or can be independently selected from group(a) as defined above or group (b) as defined above.

In some embodiments, R₁ and R₆ can be members independently selectedfrom: group (a) as defined above; group (b) as defined above, or (c)hydrocarbyl groups or substituted hydrocarbyl groups, wherein thehydrocarbyl groups or substituted hydrocarbyl groups have from about 13to about 40 carbon atoms and comprise carboxamides, carboximides,polycarboxamides, polycarboximides, carboxamidines, carboximidines,carboxylic esters, polycarboxylic esters, carboxylic acids,polycarboxylic acids, carboxylates, polycarboxylates, or combinationsthereof. In some preferred embodiments, at least one of R₁ or R₆ is amember of group (c), and can further comprise a cyclo hydrocarbyl ringor a heterocyclic ring

In polycationic carboxylates of the present technology, anions A₁ ⁻ andA₂ ⁻ can be independently selected from: (i) negatively chargedinorganic ions; (ii) organic molecules with one or more negativelycharged functional groups; or (iii) negatively charged functional groupswhich are part of R₂, R₃, R₄, R₅ or R₇. In some particularly preferredembodiments, A₁ ⁻ or A₂ ⁻ is a negatively charged functional group whichis part of R₇.

Preparation of a PCC of the Present Technology can Begin with aPrecursor, Such as either a random or structurally defined poly-cationicquat prepared by the methods described above. If an alcohol solvent hasbeen used in preparing the precursor, the alcohol solvent must beremoved by distillation, thin film evaporation, or any other suitablemethods for removal of volatile solvents. Preferably, the precursor isprepared in a non-alcoholic solvent, such as acetone or methyl ethylketone (“MEK”). Water contained in the precursor solution must also beremoved. Water removal (“drying”) can be affected by azeotropicdistillation of solvent from the precursor solution. Preferably,distillation is continued until the water content is about 0.5% or lessof the active ingredient concentration (% wt.). Dry solvent can be addedto replace the solvent and water removed during the drying process on anequal weight basis in order to maintain the active ingredientconcentration. Water content can be determined by Karl-Fisher titration.

Once the precursor solution is dry, one mole of dicarboxylic acidanhydride can be charged to the solution. If the PCC is to be providedas a tertiary amine salt, then the tertiary amine may be charged at thispoint, also. If the PCC is to be provided as a metal salt, or an aminethat would react with the anhydride functionality is used, theneutralization of the carboxylate can be obtained after the acylationstep is completed in the pH adjustment step. The mixture can be heatedto from about 30° C. to about 100° C. to facilitate dissolution andreaction of the acid anhydride. Completion of the acylation reaction canbe determined by titration. As will be understood by those skilled inthe art, the specific titration required depends on the form of thecarboxylate, which can be in either acid or salt form. Once acylation iscompleted (preferably about 90% molar conversion to ester), propertiessuch as actives concentration and pH can be adjusted (if desired)through the addition of solvents (for actives) and acids or bases (forpH adjustment).

Reaction Scheme 9 above shows an exemplary PCC which is obtainedconcurrently with the formation of the polycationic molecule. Analternate method of preparing this PCC is to prepare the GQ as inReaction Scheme 2, and then acylate the hydroxyl group withortho-phthalic anhydride in a separate step. An anhydride is employed ineither method, and any solvents used must be dry and not react with theanhydride.

Exemplary Applications of Polycationic Quat Compositions

Polycationic compounds of the present technology are suitable for a widevariety of applications where thickened or gelled aqueous compositionsare desired, including in agriculture, cleaners, personal care,disinfectants, gene transfer, etc.

For example, sprayed pesticides sometimes utilize additives to minimizespray drift. Some polycationic compositions of the present technologycan be used as drift control agents to reduce spray drift.

For another example, gels formed from polycationic compositions of thepresent technology can be used to suspend granular pesticides, and otherwater insoluble agents. It is known that certain pesticides can be usedin acid or acid salt form, such as the herbicide2,4-dichlorophenoxyacetic acid. An acid pesticide can be incorporatedinto a process for preparing polycationic compositions of the presenttechnology, such that the pesticide acid provides at least a portion ofthe counter ions to the cationic sites. Such compositions aremultipurpose, in that the viscous gel will stick to leaves of the targetplants to deliver more efficiently the herbicidal component. Suchcompositions can also be formulated with less volatile organic compoundsand other inert ingredients (that are released into the environment)than are in current commercial products.

Some polycationic compositions of the present technology can be used incleaners and cleansing gels to improve contact on vertical surfaces. Forexample, polycationic quats of the present technology can substitutepolysaccharides in cleansing gels as those described in U.S. Pat. App.No. 2004/0097385, to Chen, et al., published on May 20, 2004, or can beused to make phase stable viscoelastic cleaning compositions as thosedescribed in U.S. Pat. No. 5,833,764, to Rader, et al., issued on Nov.10, 1998, for opening drains.

Some polycationic compositions of the present technology can be used inpersonal care compositions, such as gel soaps, shampoos andconditioners. Some embodiments of polycationic compositions of thepresent technology can form stable aqueous viscoelastic solutions inwater. In some embodiments, such viscoelastic solutions are clear,instead of hazy, opaque, or pearlescent, which can result in enhancedaesthetic properties in personal care compositions. Some embodiments ofpolycationic compositions of the present technology can provide orenhance conditioning properties in personal care compositions for skinand/or hair, such as rinsability, combability (on wet and/or dry hair),feel (on skin and/or hair), detangling, and static control. With respectto specific personal care compositions, some embodiments of polycationiccompositions of the present technology can be used to substitute forsome or all of the surfactants in aqueous viscoelastic surfactantsolutions for the cleaning of hair or skin as those described in U.S.Pat. No. 5,965,502, to Balzer, issued on Oct. 12, 1999.

In at least one embodiment, a personal care composition usingpolycationic quats of the present technology can comprise a clearviscoelastic composition comprising water and least one polycationicquaternary ammonium compound comprising a bis-quaternary compound of thefollowing general formula:

In the above formulation, R₂, R₃, R₄, and R₅ can be membersindependently selected from: (a) hydrocarbyl groups having from about 1to about 4 carbon atoms; or (b) substituted hydrocarbyl groups havingfrom about 1 to about 4 carbon atoms. Alternatively, R₂ and R₃ can bemembers of a heterocyclic ring, and R₄ and R₅ can be members of adifferent heterocyclic ring or are independently selected from group (a)as defined above or group (b) as defined above. In the polycationic quatstructure, R₇ can be a member selected from the group consisting ofhydrocarbyl groups having from about 2 to about 30 carbon atoms, orsubstituted hydrocarbyl groups having from about 2 to about 30 carbonatoms. Additionally, R₁ and R₆ can be members independently selectedfrom group (a) as defined above; group (b) as defined above, or (c)hydrocarbyl groups having from about 13 to about 40 carbon atoms orsubstituted hydrocarbyl groups having from about 13 to about 40 carbonatoms. At least one of R₁ or R₆ should be a member of group (c) asdefined above. Further, the anions, A₁ ⁻ and A₂ ⁻ can be independentlyselected from (i) negatively charged inorganic ions; (ii) organicmolecules with one or more negatively charged functional groups; or(iii) negatively charged functional groups which are part of R₁, R₂, R₃,R₄, R₅, R₆, or R₇.

The ability of viscoelastic solutions using polycationic quats of thepresent technology to form stable suspensions having particulatematerial suspended therein is also beneficial in the personal care area.Examples of particulates include, for example, but are not limited to,anti-dandruff agents, abrasives (e.g., crushed walnut or apricot shells,silica, cellulose), sun block agents (e.g., zinc oxide), pigments anddyes, glitters, and micro-encapsulated materials (e.g., vitamins,minerals, fragrances, polymer beads), can be used in formingviscoelastic suspensions in personal care compositions.

Bleaching agents such as hydrogen peroxide can be gelled usingpolycationic compounds of the present technology to make thickenedaqueous bleach compositions. For example, U.S. Pat. No. 4,800,036,issued Jan. 24, 1989 and European Patent No. EP 0298172, issued on Jan.11, 1989, both to Rose, et al., teach aqueous bleach compositionsthickened with a viscoelastic surfactant. Some polycationic quats of thepresent technology can be used for such applications. Some quaternarycompounds of the present technology also have bactericidal properties.

The thickening and viscoelastic properties of viscoelastic compositionsof the present technology may be related to vesicle formation, or otherphenomena. As shown in FIGS. 14 and 15, some polycationic quats of thepresent technology have demonstrated vesicle formation.

As known in the art, micelles demonstrate a variety of forms, such asrod or worm-like. A key characteristic of micelles is that thesurfactant molecules that make up the micelles are oriented such thatthe hydrophilic portions of the molecules form the outer surface aroundan internal core region, in which the hydrophobe portions of themolecules reside. The radius of the core is approximately equal to thelength of the fully extended hydrophobe chain. The average number ofsurfactant molecules in a micelle is the aggregation number, and canrange from several molecules to over a hundred for typical cationicsurfactants. Micelles are dynamic structures in equilibrium with freesurfactant molecules in solution. Surfactant molecules exchange into andout of micelles with high frequency. Because micelles are too small tobe seen by light microscopy, electron microscopy is used.

Vesicle formation can provide additional useful properties other thanthickening. Vesicles are more or less spherical surfactantself-assemblies. Essentially, a vesicle is a bilayer lamellar structurein which the edges have wrapped around and joined each other to form asphere. Vesicles may have multiple bilayers, which creates concentricspheres. The core of a vesicle is a compartment that contains theaqueous solvent used to dissolve the surfactant initially, butessentially free of surfactants molecules. Vesicles may be manipulatedin such a way that the internal compartment is used as a carrier forother molecules. The number of surfactant molecules that make upvesicles is much larger than are in micelles, usually about 10 to about1000 times larger. Furthermore, although vesicles are also dynamicstructures, the rate of exchanges of surfactant molecules in vesiclesare much slower than those in micelles. As Zana describes vesicles atpage 26 of Dynamics of Surfactant Self-Assemblies (2005), “the lifetimeof a vesicle must be extremely long and vesicles can probably beconsidered as “frozen” on the laboratory times scale (weeks to months oryears)” Many vesicles are large enough to be seen under a lightmicroscope.

Another key feature of vesicles is that a vesicle has an inside and anoutside. The inside encloses some of the aqueous phase, and possiblyother molecules dissolved in the water. Vesicles can be used to deliverentrapped molecules into environments they might not normally haveaccess to because of chemical instabilities, etc. In contrast, theinterior of a micelle is in a “quasi-liquid state” according to page 14of Dynamics of Surfactant Self-Assemblies, by Zana.

Spontaneous vesicle formation has been observed for GQs and PCCs of thepresently described technology under a light microscope (see FIGS. 14and 15). Vesicle formation has been observed when polycationic compoundsare exposed to either dilute salt solutions or dilute solutions ofanionic surfactant. PCCs have been observed to form vesicles indeionized water.

In the area of gene transfer, vesicles are synthetic analogs ofliposomes—essentially naturally occurring biological vesicles. Syntheticvesicles can be infused with, for example, drug molecules. The vesiclescan then be used to deliver the drug as part of treatment. Cationicvesicles have been found to be useful in gene therapy for the deliveryof genetic material. However, conventional alkylamine and etheraminecationic compounds exhibit toxicity to many organisms that limits theirin vivo use, while esteramine derived cationic compounds are less toxic,but also less stable. The amidoamine polycationic quats of the presenttechnology have demonstrated vesicle formation and can be less toxicthan alkylamine quats but more stable than esteramine derived quats.

Besides fracturing fluids as described earlier in this application, somepolycationic compounds of the present technology can be used in otherhydrocarbon recovery fluids in oil field, which include, for example,other stimulation fluids (such as acidizing fluids), drilling fluids,thickeners, completion fluids, diversion fluids, etc.

In oil field applications, acidizing is a process of pumping acid into awell bore to remove formation damage or other materials so thatproduction is enhanced. In this process, thickened acids are desirablebecause they provide more efficient acidizing in certain types ofsubterranean zones, e.g., high permeability formations. Other acidizingapplications use invert emulsions of aqueous acid in an oil, e.g.,diesel or kerosene. Some polycationic compounds of the presentlydescribed technology as described above can be used as acid thickenersor to form invert emulsions with acid and oil.

Certain polycationic quat compositions of the present technology canalso be used in drilling fluids. The special class of drilling fluidsused to drill most deep wells is called drilling muds because of theirthick consistency. Drilling muds normally require additional propertiesbeyond simple drilling fluids that can prevent damage to thesubterranean formation, prevent drill pipe corrosion and fatigue, andallow the acquisition of information about the formation being drilled.Drilling fluids and muds may be subclassified according to a number ofcharacteristics, such as fluid phase alkalinity, water or oil continuousphase, etc. Besides polycationic quats of the present technology,drilling mud compositions can further include the traditionalingredients such as bactericides, corrosion inhibitors, emulsifiers,fluid loss and viscosity control agents, shale control additives, etc.

Water based drilling fluids use various polymers as thickeners toincrease the viscosity of the drilling fluids and improve the fluidsability to remove cuttings. Some polycationic quats of the presentlydescribed technology can be used as thickeners for such drilling fluidsor muds.

Thickeners suitable for use in oil based drilling fluids includeorganoclays. These are clays treated with various compounds to make themcompatible with organic fluids. When placed in an oil based drillingfluid, they thicken the fluid, improving the fluids ability to carry thecutting to the surface. Some polycationic compositions of the presenttechnology can be used as treatment compositions for making organoclays.

Some drilling fluids are water in oil emulsions. These emulsions ofteninclude brines which can adjust the density of the drilling fluid.Controlling the density of the drilling fluid is important to preventformation damage and lose of drilling fluid. High density drillingfluids provide support to the surrounding formation that, under its ownpressure, might collapse into the bore hole if lower density fluids wereused. Formation preparation and hydrocarbon recovery would then be morecomplicated. The high electrolyte strength of high density brines canalso reduce the permeation of well bore fluids into the formation (whichmust later be recovered), and they may reduce the hydration of shale andclay in the formation. Some polycationic quats of the present technologycan be used for thickening or emulsifying the brines in the drillingfluids.

During the drilling operations, the subterranean formation and well borecasing come into contact with a variety of materials which can haveadverse effects on further operations or hydrocarbon production. Thecasing pipe needs to be cemented and the cement needs to adhere to theformation and various materials used in the drilling fluid can preventthis. Completion fluids are used to wash these materials from theformation. Since the density of the completion fluids can affect thewell bore similarly to the drilling fluids above, a variety of brines orother materials are used. Hydrocarbons, olefins, etc. are circulated toremove the oil based muds. Gelled pills are added to push thesematerials through the well. The gel forming properties of certainpolycationic compounds of the present technology can providecompositions for these applications. Furthermore, gel pills are pushedthrough the well with other fluids such as brines, which may requireviscosity modification. Some polycationic compounds of the presenttechnology have shown to provide such viscosity modification to avariety of brines and water.

Another function of the completion fluid is to remove particulate matterand remnants of other materials used in the drilling operation from thecasing, such as pipe dope. The various materials added to pipe dope canplug the formation and cause damage to the production zones. As thesematerials are removed from the joints in the casing string, they cansettle out in the production zone. By viscosifying the completion fluid,this kind of settling can be minimized. Furthermore, the filter cakeformed during the drilling operation often requires special treatments,such as enzymes or hydrogen peroxide, to effect sufficient removal. Somepolycationic compound compositions of the present technology can provideuseful, new or improved compositions for formulation of filter cakeremoval treatments.

Some completion fluids such as those that use zinc bromide, cesiumbromides/chlorides, or formate brines are very expensive. In order toget the required cleaning/debris removal, large volumes areconventionally required. Some polycationic compounds of the presenttechnology can be used as gelling agents for these expensive compoundsto decrease the volumes required by decreasing the amount of expensivebrines that leak off into the subterranean formation (often causingformation damage).

Subterranean formations have different properties, such as differentpermeability, that can affect the ways in which matters flow into andout of the formations. Certain chemicals can alter the permeability byforming gels that can block matter transport through more porous zones.The matter transport is then diverted to other zones, from whichhydrocarbon may be recovered, or into which additional treatments may beapplied (e.g. acidizing). Some polycationic compounds of the presenttechnology can be used as gelling agents in such diversion fluids.

Certain polycationic compositions of the present technology can also beused as additives for various processes in hydrocarbon recovery, forexample, in fluid loss control, corrosion inhibition, scale inhibition,clay stabilizing, drag reducing, demulsifying, gas hydrate control, etc.

Fluid loss additives, or filtrate-reducing agents, are often used tominimize the loss of process fluids into the formations during variousprocesses, e.g. drilling or fracturing. This helps avoid certain typesof formation damage and reduces the expense of lost process fluids, someof which have high cost. Conventionally, fluid loss prevention can bedivided into three categories by mechanisms, where (1) macroscopicparticles clog the formation pores to form a filter cake with reducedpermeability, (2) microscopic particles form a gel in the boundary layerbetween the fluids and the porous formation, and (3) a chemical resin isinjected and cured irreversibly in the formation. Some polycationiccompounds of the present technology can be used as fluid loss additivesthat can form a gel in the boundary layer to prevent fluid loss.

Corrosion and scale deposition are the two of the most costly problemsin oil industries. Corrosion may occur not just in stimulation andrecovery operations, but in transport and refining operations also. Somepolycationic quaternary ammonium compounds of the present technology canprovide useful, new or improved compositions for corrosion inhibitionacross the various hydrocarbon related operations.

Scale deposition also occurs in various operations in the petroleumindustry. Scales may contain carbonates of calcium and iron, sulfates ofbarium and strontium, iron oxides and sulfides, and magnesium salts.Scale inhibitors may act as thermodynamic inhibitors by reacting orcomplexing with scale forming substances so that a chemical equilibriumis established that suppresses crystal growth. Polyamines, quaternaries,aminosulfonates and aminophosphonates are a few examples of chemicalclasses of scale inhibitors. Surfactants may also act as scaleinhibitors by suppressing the adherence of crystals to metal surfaces.Some polycationic compounds of the present technology provide useful,new or improved scale inhibitors in each of these classes.

It is known that swelling due to clay or shale hydration in subterraneanformations is one of the most important causes for borehole instability.Clays may swell as a result of surface hydration, or from osmoticpressure due to cation concentration gradients between the clay andsurrounding water. Some polycationic compounds of the present technologyprovide useful and new clay stabilizers that can inhibit or reduce shalehydration.

In oil field, chemical additives that can reduce drag are used, forexample, in pipelines for liquid transportation, in drillingapplications and in fracturing. The drag on a fluid as it flows throughpipes or down bore holes limits the pressures that may be attained,increases equipment demands and costs, and increases energy demands.Certain cationic surfactants are known to be drag reducing agents, andviscoelasticity is also frequently associated with drag reduction.Polymers are also used as drag reducers, but when they are used, oneserious problem in the effectiveness of drag reducers is the chaindegradation of polymers by shear strains in turbulent flow. Somepolycationic compounds of the present technology provide drag reducerswhich do not suffer the degradation by shear strains.

When crude oil is produced, most of it occurs emulsified with water.Chemical demulsifiers are used to separate the water from thehydrocarbons before transportation. At refineries, crude oil issometimes emulsified in fresh water, followed by demulsification, toreduce the salt content of the crude oil. Some polycationic compositionsof the present technology can provide useful, new or improvedcompositions that can be used as demulsifiers.

Further, the polycationic compositions of the present technology canalso function as gas hydrate inhibitors, either as crystal inhibitors orthrough other mechanisms. Gas hydrates are types of clathrates in whichwater and hydrocarbons form crystalline addition compounds. The hostcompound, water, forms crystals, and the guest compound, hydrocarbonssuch as methane, are held in free spaces between the water crystals. Gashydrates can form in pipelines, forming solid deposits that reduce pipediameter or even clog them. Some polycationic quats of the presenttechnology can inhibit the formation of gas hydrates.

The present technology will be better understood by reference to thefollowing examples. These examples are provided to describe specificembodiments of the invention and to demonstrate how they work. Byproviding these specific examples, the inventors do not limit the scopeof the invention. It will be understood by those skilled in the art thatthe full scope of the invention encompasses the subject matter definedby the claims concluding this specification, and any equivalents of theclaims.

EXAMPLES Example 1 Synthesis of Structurally DefinedSoyAPDMA-3(OH)-18APDMA

A 1000 ml 5-necked glass flask was charged with about 40 g of deionized(DI) water, about 91.4 g of 2-propanol, 179 g ofstearamidopropyldimethylamine (SAPDMA) (482.5 mmol) and 91.8 g ofpara-toluenesulfonic acid (“PTSA”) dihydrate (482.5 mmol). The mixturewas mixed and heated to approximately 50° C. About 46 g (497 mmol) ofepichlorohydrin was added to the reactor dropwise during 2 hours withthe reactor still at approximately 50° C. The pH value of the reactionmixture changed from about 4.5 (when the addition of epichlorohydrinstarted) to about 4.85 (when the addition finished).

After holding the reaction mixture at approximately 50° C. for anadditional 2 hours, the pH became 5.17. The temperature of the solutionwas then increased to approximately 70° C. About 173 g (482.5 mmol) ofsoyamidopropyldimethylamines (SoyAPDMA) were added dropwise to thereactor. The pH value of the reaction solution was monitored so that pHdid not exceed 8.0. The SoyAPDMA charge was completed in 30 minutes, andthe pH never exceeded 7.0 during that time. The solution was held atapproximately 70° C. for 2 hours. The reaction solution was then cooledand left standing overnight before being sampled for free amine andamine hydrochloride as follows.

Titration with KOH followed by HCl revealed that the reaction mixturehad an amine salt (as the chloride) content of about 4%. Free aminecould not be titrated because tosylate interferes with titration by HCl.Instead, about 5 g epichlorohydrin was added to consume the unreactedamine salt. The reaction mixture was held for about 2 hours atapproximately 70° C., and was then titrated again. The resultant contentof amine salt (as chloride) was about 2%. The reaction mixture wascooled, and its pH value was 6.8. Several drops of 20% HCl were addeduntil pH was about 6. Solids analysis on a moisture balance showed asolid content of about 60.2%.

This example produced a structurally defined Gemini quat (GQ) in whichone amine mixture was saturated and the other was largely unsaturated.

Example 2 Synthesis of Symmetric HERAPDMA-GQ

About 119 g 2-propanol and 177.4 g of high erucic rapeseedamidopropyl-N,N-dimethylamine (HERAPDMA) were added to 1000 ml 5-neckedflask. A mixture of about 24.3 g of a solution of 37% HCl by weight and5.7 g water was added to the flask dropwise over approximately 15minutes with vigorous stirring and air cooling to minimize heating. Atthe end of addition, the temperature of solution reached 55° C., and thepH was 7.2. The addition funnel well was rinsed with water, and thenepichlorohydrin was added during a 90 minute period, and the pH wascontinuously monitored. The temperature of the solution when theepichlorohydrin addition started was approximately 50° C. Thetemperature of the reaction solution rose to approximately 67° C. overthe first hour and then remained there for about another 45 minutes,after which the temperature began to drop. Heating was then provided toincrease the temperature to about 70° C., and heating was held for 4hours prior to being shut down.

A sample of the resultant reaction solution was titrated for aminehydrochloride and free amine. The result showed that the reactionsolution contained 4.0% of salt and 3.07% of free amine by weight basedon the total weight of the solution sample. An additional 10 gepichlorohydrin was added. After the reaction solution was held at 70°C. for approximately 2 hours, the heat was turned off. After another 2hours, the resultant solution was sampled for free amine and amine saltagain. It contained about 2% free amine and amine salt combined (1.01%and 0.98% respectively). The pH value was about 6.7. Several drops of20% HCl were added to adjust the pH to about 5.5.

Example 3 Synthesis of HERAPDMA-PCC

167 g of the product of Example 2 containing 100 g (118 mmol) ofHERAPDMA-GQ were stripped of water and alcohol solvent by distillingthem from the solution under a vacuum on a thin-film rotary evaporator.Three portions of MEK solvent (100 g) were distilled from the mixture toobtain a water level of 0.3% (determined by Karl-Fisher titration).Then, about 17.5 g (118 mol) of o-phthalic anhydride were added to themixture with about 12 g (121 mmol) triethylamine. The mixture was thenheld at reflux at about 88° C. for one hour. The anhydride dissolvedwithin the first 15 minutes and a clear solution was attained.

After the mixture was held at reflux at about 88° C. for an hour, thesolution was cooled. A small sample was taken and the solvent wasevaporated from the sample. An IR spectrum of the dried residue clearlyshowed an ester signal but no anhydride signal was detectable.

The reaction mixture was again placed on a thin-film rotary evaporatorand the excess triethylamine and a portion of the MEK were removed. Athick, cloudy mixture was obtained that was then diluted with about 45 gmethanol to obtain a clear amber solution with a solids content of about50.1%. This solution was then used for preparing viscoelastic gels.

Example 4 Synthesis of a Non-Gemini HERAPDMA Bis-Quat

About 50.6 g water, 84.2 g 2-propanol, and 145.8 g HERAPDMA were addedto a 500 ml 5-necked flask with stirring, nitrogen, reflux and a pHprobe. Next, about 40 g 37% HCl was added slowly to the mixture withvigorous stirring. The reaction mixture was heated to 50° C., and thenabout 38.3 g epichlorohydrin was added slowly during a period ofapproximately 45 minutes. The reaction mixture was then held atapproximately 50° C. for 2 hours, and was then further heated toapproximately 70° C. About 41.1 g triethylamine (TEA) was then chargedslowly to the reaction mixture through the addition funnel. The pH valueof the reaction mixture was monitored closely to ensure that it did notexceed 8.0. The TEA addition was completed in about 30 minutes, and thepH value did not exceed 7.8. The reaction mixture was then held atapproximately 70° C. for 2 hoursprior to being sampled for free amineand amine hydrochloride. The sampling showed that the resultant reactionmixture contained 3.2% free amine and 2.1% amine hydrochloride (asHERAPDMA and its salt).

Next, another 5 g of epichlorohydrin was added to the reaction mixture.The reaction mixture was held for another hour at 70° C., and thensampled for free amine and amine salt again. The result was essentiallyunchanged and showed that the mixture contained about 3.1% amine and2.0% salt. The reaction mixture was cooled, and its pH was adjusted to5.5 with several drops of 20% HCl at 40° C. The non-gemini HERAPDMAbis-quat produced can be represented by the following formula:

Comparative Example 5

In this comparison, 13 viscoelastic solutions were made from 8polycationic quats of the present technology (Compounds 1-8 below), andwere compared against a viscoelastic solution containing Schlumberger'scommercially available cationic VES product ClearFRAC™ (EHMAC). Themolecular structure of EHMAC is shown in FIG. 5 b.

The 8 compounds of the present technology that were used in this testingare as follows:

-   Compound 1 Gemini stearamidopropyldimethylammonium di-chloride    (18APDMA-3(OH)-18-APDMA or SAPDMA GQ). (illustrated in FIG. 6 b).-   Compound 2 Gemini (cetyl/oleyl)amidopropyldimethylammonium    di-chloride (16APDMA/18:1APDMA)-3-(OH)-(16APDMA/18:1APDMA).    (illustrated in FIG. 7 b, where R═C₁₄H₂₉ and C₁₆H₃₁ (linear)).-   Compound 3 Dissymmetric gemini    oleamidopropyldimethylammonium-stearamidopropyl-dimethylammonium    di-chloride (18:1APDMA-3-(OH)-18-APDMA). (illustrated in FIG. 8 b,    where R₁═C₁₆H₃₃ (linear) and R₂═C₁₆H₃₁ (linear)).-   Compound 4 Dissymmetric gemini    soyamidopropyldimethylammonium-stearamidopropyl-dimethylammonium    chloride toluene sulfonate (SoyAPDMA-3-(OH)-18APDMA). (illustrated    in FIG. 9 b, where R₁═C₁₆H₃₃ (linear)). SoyAPDMA is a mixture mostly    of (in order of decreasing amounts): 18:2 APDMA, 18:1APDMA, 16APDMA,    18:3 APDMA, 18APDMA-   Compound 5 Gemini high erucic rapeseed amidopropyldimethylammonium    di-chloride (HERAPDMA-3-(OH)—HERAPDMA or HERAPDMA GQ). (illustrated    in FIG. 10 b, where R is derived from high erucic rapeseed oil, in    which at least 40% of fatty acid chains are erucyl). Common    components of HERAPDMA include: 22:1APDMA, 18:2 APDMA, 18:1APDMA and    18:3 APDMA-   Compound 6 Dissymmetric gemini behenamidopropyldimethylammonium-high    erucic rapeseed amidopropyldimethylammonium di-chloride    (22APDMA-3-(OH)—HERAPDMA). (illustrated in FIG. 11 b, where R₁ is    derived from high erucic rapeseed oil, in which at least 40% of    fatty acid chains are erucyl, and R₂═C₂₀H₄₁ (linear)). Common    components of HERAPDMA include: 22:1 APDMA, 18:2 APDMA, 18:1 APDMA    and 18:3 APDMA.-   Compound 7 Dissymmetric bis-Quaternary (BQ) high erucic rapeseed    amidopropyl-dimethylammonium-triethylammonium di-chloride.    (illustrated in FIG. 12 b, where R₁ is derived from high erucic    rapeseed oil, in which at least 40% of fatty acid chains are    erucyl). Common components of HERAPDMA include: 22:1APDMA, 18:2    APDMA, 18:1APDMA and 18:3 APDMA.-   Compound 8 Poly-cationic carboxylate (PCC) bis-high erucic rapeseed    amidopropyldimethylammonium di-chloride phthalate half-ester,    triethylammonium salt. (illustrated in FIG. 13 b, where R is derived    from high erucic rapeseed oil, in which at least 40% of fatty acid    chains are erucyl). Common components of HERAPDMA include:    22:1APDMA, 18:2 APDMA, 18:1APDMA and 18:3 APDMA.

The table below summarizes the viscoelastic gels prepared and tested inthis example. One viscoelastic gel was made containing EHMAC.Additionally, one viscoelastic gel was made from each of Compounds 1, 2,3, 6 and 8. Two viscoelastic gels, that differed in the weightpercentage of the gellant and the additive, were made using each ofCompounds 4 and 5. Three viscoelastic gels, that differed in the weightpercentage of the gellant and the additive, were made using Compound 7.

Each viscoelastic gel was prepared by adding the specified weightpercentages of compound (gellant) and additive to an electrolytesolution in a blender cup. The mixture was then blended on a commercialduty Waring blender for about from 1 to 3 minutes. Blends were made atroom temperature, but the mechanical energy of the mixing process tendedto warm them slightly. The resultant gel contained a large amount ofentrained air, which was removed prior to rheology testing bycentrifugation, heated ultrasonication, or combinations of both.

The electrolyte level for each viscoelastic composition is listed in thetable below. In solutions for viscoelastic gels, tap water can be usedas the solvent instead. The electrolyte solutions were prepared bymixing the salts with water and stirring a few minutes.

The viscoelastic solution containing EHMAC was prepared according to thedescription of U.S. Pat. No. 5,551,516, to Norman et al., at column 10,paragraph 35, through column 12, paragraph 40. The optimum saltconcentration for highest viscosity with the EHMAC viscoelastic solutionwas determined to be about 4% KCl.

WT % SCREEN- ADDITIVE ING GELLANT WT % ADDI- (ELECTRO- VISCOS- COMPOUNDGELLANT TIVE LYTE) ITY (CP) FIG. EHMAC 3.00% KCl 4.00% 35  5a 1 3.00%KCl 1.50% 250  6a 2 3.00% KCl 1.50% 60  7a 3 3.00% KCl 1.50% 293  8a 43.00% KCl 0.75% 317  9a 4 1.25% KCl 1.50% 74  9c 5 3.00% SXS 0.50% 16910a 5 2.00% KCl 1.50% 168 10c 6 3.00% KCl 2.00% 276 11a 7 4.00% CaBr225.00% 53 12a 7 2.50% CaBr2 25.00% 125 12c 7 2.75% CaBr2 6.00% 70 12d 83.00% none none 274 13a

Screening viscosity was the viscosity at 90° C. and a shear rate of 100sec⁻¹. This is referred to as the screening viscosity, because a guidingcriterion for assessing gellants for fracturing processes is theviscosity of its gel at approximately 85° C. and a shear rate of 100sec⁻¹. The generally accepted viscosity requirement for a VES underthese conditions is about 100 cP (0.1 Pa·s).

Small amplitude oscillatory shear (SAOS) experiments were used tomeasure elastic properties of each of the viscoelastic compositionsreferenced in the table above. In this experiment, a sinusoidal imposedsmall strain was used to induce a sinusoidal measured stress and thuscause formation of shear-induced structures of gellant aggregates. Thetheory and methods are described in detail in Dynamics of SurfactantSelf-Assemblies (Chapter 9; Surfactant Science Series Volume 125, editorRaul Zana). Each of the tested viscoelastic compositions was observed toposses elastic properties, i.e., the value of the elastic storagemodulus (G′) was equal to or greater than the value of the viscous lossmodulus (G″) at a frequency characteristic for each composition.

Measurements of the relationships between shear rate, viscosity andtemperature that were made for each viscoelastic gel to create flowcurves. The rheometer used for each of the tests was an AR2000 from TAInstruments. The geometry used was a DIN concentric cylinder. Viscositywas measured (approximately every 10 seconds) as the shear rate wasstepped from 0.0015 to 150 sec⁻¹ over a period of approximately 3minutes while the temperature was held constant. A flow curve wasobtained at three temperatures (i.e., 30° C., 60° C. and 90° C.) foreach sample. The Figures referenced in the table above illustrate theflow curves based upon those measurements.

As indicated in the table above, each of the viscoelastic compositionsof the present technology (with Compounds 1-8) provided higher viscositythan did EHMAC under the screening conditions. of the resultsillustrated in FIGS. 5 a-13 a also reveals unexpected and usefulproperties conferred by several of the embodiments of these inventions,including, for example:

Small or no decrease in viscosity as temperature increased across therange measured;

Lower requirements for gellant active ingredient;

Lower or no requirement for additives; or

Solubility and thickening of high salt concentration solutions.

Referring to FIG. 6 a, Compound 1 of the present technology (SAPDMA GQ)demonstrated unexpected lower viscosity at 30° C. vs. 60° C. and 90° C.curves. The 90° C. viscosity of the SAPDMA GQ viscoelastic solutionexceeded that of the benchmark VES (see FIG. 5 a) by more than 100%across the range of shear rates.

FIG. 7 a shows that the VES of Compound 2((16APDMA/18:1APDMA)-3-(OH)-(16APDMA/18:1APDMA)) demonstrated anexpected temperature—viscosity profile (decreasing viscosity withincreasing temperature). The GQ VES viscosity at 90° C. (FIG. 7 a)exceeded the viscosity of the 3% EHMAC VES at 90° C. (FIG. 5 a) acrossthe range of shear rates.

FIG. 8 a shows that the VES of Compound 3 (18:1 APDMA-3-(OH)-18APDMA)unexpectedly demonstrated very little temperature sensitivity from 30°C. to 90° C. This dissymmetric GQ VES had comparable viscosity to theVES of Compound 1 (SAPDMA GQ) at equal concentrations and temperatures,as shown by FIGS. 6 a and 8 a. However, unlike the SAPDMA GQ, which wasa solid even at 45% actives in alcohol/water, this dissymmetric GQ ofCompound 3 was a clear liquid at 60% actives in alcohol and water.Again, the viscosity of this VES exceeded that of the EHMAC VESsubstantially.

FIG. 9 a shows the flow curves of the first viscoelastic solutionprepared from Compound 4 (SoyAPDMA-3-(OH)-18APDMA), which was a 3% GQsolution in 0.75% KCl (wt/wt %). This VES showed a viscosity profilesimilar to that of the VES from Compound 3 (see FIGS. 8 a and 9 a).However, the benefit of a lower salt (KCl) requirement was achieved inCompound 4 through use of toluene sulfonic acid in place of hydrochloricacid in the synthesis. This VES with Compound 4 used less than 20% ofthe amount of KCl required by the EHMAC VES (see FIG. 5 a), yet achievedsuperior results over the EHMAC VES. Like Compound 3, Compound 4 wasobtained in an easily handled liquid at 60% actives.

FIG. 9 c shows the flow curves of the second viscoelastic solutionprepared from Compound 4, which contained 1.25% GQ in 1.5% KCl solution(wt/wt %). This second VES using Compound 4 demonstrated a substantiallylower requirement for gellant when 1.5% KCl by weight was used. This VESfrom Compound 4 required less than 45% of the gellant and 50% lesspotassium chloride to obtain a viscosity profile superior to that of theEHMAC benchmark (see FIGS. 5 a and 9 c).

FIG. 10 a shows the flow curves of the first viscoelastic solutionprepared from Compound 5 (HERAPDMA GQ), which contained 3% GQ in a 0.5%sodium xylene sulfonate (SXS) solution (wt/wt %). HERAPDMA GQ was aliquid at 60% actives. An unexpected benefit demonstrated in thisviscosity profile was a low sensitivity to temperature from about 30° C.to about 90° C.

The second VES based on HERAPDMA GQ (Compound 5) used 1.5% KCl in placeof the SXS, and also used ⅔ the amount of gellant used in the EHMAC VES.The flow curves of this VES are shown in FIG. 10 c. Again, the viscosityprofile of this VES showed only small viscosity changes across thetemperature range of about 30° C. to about 90° C.

FIG. 11 a shows the flow curves for the viscoelastic solution preparedfrom Compound 6 (22APDMA-3-(OH)—HERAPDMA), which contained 3% GQ in a 2%KCl solution (wt/wt %). This VES based on Compound 6 provided viscositymore than triple that of the EHMAC VES at 900° C. across the range ofshear rates (see FIGS. 5 a and 11 a).

FIG. 12 a shows the flow curves of the first viscoelastic solutionprepared from bis quat (BQ) Compound 7, which contained 4% BQ in a 25%CaCl₂ solution (wt/wt %). The density of 25% CaCl₂ at 25° C. was about1.24 g/ml. The flow curves in FIG. 12 a show that the singlehydrophobe-bis-quaternary compound of the present technology provideduseful VES properties in solutions with higher salt concentrations thanused for the VESs of the GQs of the present technology or the EHMACgellant. This example demonstrates that dissymmetric single hydrophobeBQs can confer VES properties in high density brines, which are commonlyused in well bore service fluids for the benefits of their densityand/or salt effects, where the EHMAC VES normally will fail.

The flow curves of a second VES from BQ Compound 7 are shown in FIG. 12c, which demonstrated an even higher viscosity than those shown in FIG.12 a. The second VES containing 2.5% BQ in a 25% CaBr₂ solution (wt/wt%) used less gellant than that of FIG. 12 a and a different high densitybrine (25% CaBr₂ has a density of about 1.2 g/ml at 25° C.).

Thickening in high salt concentration solutions can be useful for anumber of operations besides fracturing, as described earlier in thisdisclosure.

Referring to FIG. 12 d, the flow curves of a third VES prepared from BQCompound 7 demonstrated that, besides high salt concentration solutions,dissymmetric single hydrophobe BQs can provide useful thickeningproperties across a wide range of salt concentrations. In this VES, a 6%CaBr₂ solution was used, which had a density of only about 1.05 g/ml at25° C.

A gelled, viscoelastic high-density clear brine was also prepared fromCompound 7, which contained 4% BQ in a solution of 52.8% ZnBr2, 22.8%CaBr2, and 24.4% water, and had a density of about 19 lb. per gallon at70° C. Viscosity measurements were not obtained on this solution as thebrine components are harmful to the rheometer.

FIG. 13 a shows the flow curves of a VES prepared from Compound 8, whichwas a PCC. This VES contained 3 wt % PCC in deionized water and no saltor other additive was added. The flow curves of this VES showedunexpected and useful results, because it completely eliminated therequirement for salts, cationic surfactants, or other additives. Theviscosity profile for this VES also demonstrated very little change inviscosity over the temperature range of about 30° C. to about 90° C.,and was at least 100% higher than that of the EHMAC VES (see FIGS. 5 aand 13 a).

Studying the flow curves of the viscoelastic solutions containingCompounds 1-8 of the present technology collectively, the relativeinsensitivity of viscosity to temperature across the range measuredsuggests that such compositions might provide useful thickeningproperties well above the range measured, especially in light of thedegree to which they exceed the 100 cP viscosity target under thescreening conditions.

The invention has been described above in such full, clear, concise andexact terms as to enable any person skilled in the art to which itpertains, to practice the same. It is to be understood that theforegoing describes preferred embodiments of the invention and thatmodifications may be made thereto without departing from the scope ofthe invention as set forth in the following claims.

1. A viscoelastic composition comprising water, at least onepolycationic quaternary ammonium compound to control the viscoelasticityof the composition, wherein the at least one polycationic quaternaryammonium compound comprises a bis-quaternary compound of the followinggeneral formula:

wherein R₂, R₃, R₄, and R₅ are members independently selected from thegroup consisting of: (a) hydrocarbyl groups having from about 1 to about4 carbon atoms; and (b) substituted hydrocarbyl groups having from about1 to about 4 carbon atoms; or alternatively wherein R₂ and R₃ aremembers of a heterocyclic ring, and R₄ and R₅ are members of a differentheterocyclic ring or are independently selected from group (a) asdefined above or group (b) as defined above; wherein R₇ is a substitutedhydrocarbyl group having from about 3 to about 8 carbon atoms; whereinR₁ and R₆ are independently selected from (c) substituted hydrocarbylgroups having from about 13 to about 40 carbon atoms; and wherein A₁ ⁻and A₂ ⁻ are independently selected from the group consisting of: (i)negatively charged inorganic ions; (ii) organic molecules with one ormore negatively charged functional groups; and (iii) negatively chargedfunctional groups which are part of R₁, R₂, R₃, R₄, R₅, R₆, or R₇; thecomposition further comprising at least one additive selected from thegroup consisting of inorganic salts, organic acids, salts of organicacids, poly acids, salts of poly acids, diacids, salts of diacids,anionic surfactants, anionic hydrotropes, poly-anionic polymers, andcombinations thereof; wherein the viscoelastic composition is aviscoelastic solution and wherein the combination of the at least onepolycationic quaternary ammonium compound and the at least one additiveis effective to obtain a viscosity of at least about 100 cP measured ata temperature of 90° C. and at a shear rate of 100 sec⁻¹.
 2. Thecomposition of claim 1, wherein the composition maintainsviscoelasticity at a temperature greater than about 110° C.
 3. Thecomposition of claim 1, wherein the substituted hydrocarbyl groups ofgroup (c) comprise carboxamides, carboximides, polycarboxamides,polycarboximides, carboxamidines, carboximidines, carboxylic esters,polycarboxylic esters, carboxylic acids, polycarboxylic acids,carboxylates, polycarboxylates, or combinations thereof.
 4. Thecomposition of claim 1, wherein the substituted hydrocarbyl groups ofgroup (b) have one or more substituents selected from the groupconsisting of hydroxy, alkoxy, aryloxy, carbonate ester, carbamate,sulfonate, phosphinate, phosphite, phosphate, phosphonate, andcombinations thereof.
 5. The composition of claim 4, wherein the alkoxyor aryloxy substituents have the general formula —OR, where R is ahydrocarbyl group having from about 1 to about 4 carbon atoms.
 6. Thecomposition of claim 1, wherein R₇ is hydrophilic.
 7. The composition ofclaim 1, wherein R₇ has a linear configuration.
 8. The composition ofclaim 1, wherein R₇ has a configuration comprising a ring.
 9. Thecomposition of claim 1, wherein R₇ is a substituted hydrocarbyl groupthat is not a hydroxyalkylene.
 10. The composition of claim 1, whereinthe substituted hydrocarbyl groups for R₇ have one or more substituentsselected from the group consisting of hydroxyl, alkoxy, aryloxy, estercarbonate, carbamate, sulfonic acid, sulfonate, phosphinic acid,phosphinate, phosphorous acid, phosphite, phosphoric acid, phosphate,phosphonate, and combinations thereof.
 11. The composition of claim 10,wherein the alkoxy or aryloxy substituents have the general formula —OR,where R is a hydrocarbyl group having from about 1 to about 4 carbonatoms.
 12. The composition of claim 1, wherein the bis-quaternarycompound is symmetric.
 13. The composition of claim 1, wherein R₇ isderived from a di-sulfonic acid ester of a primary diol, a secondarydiol, a derivative thereof, or a combination thereof.
 14. Thecomposition of claim 1, wherein R₇ is derived from an epihalohydrin. 15.The composition of claim 1, wherein R₇ is derived from a bis-glycidylether.
 16. The composition of claim 1, wherein at least one of R₁ or R₆is derived from a carboxylic acid having from about 13 to about 40carbon atoms.
 17. The composition of claim 1, wherein the at least onepolycationic quaternary ammonium compound is less than about 10% byweight based on the total weight of the composition.
 18. The compositionof claim 1, wherein the inorganic salt is selected from the groupconsisting of sodium chloride, potassium chloride, ammonium chloride,calcium chloride, sodium bromide, calcium bromide, zinc bromide,potassium formate, cesium chloride, cesium bromide, and combinationsthereof.